Polymer film, retardation film, polarizing plate, liquid crystal display, and compound

ABSTRACT

Provided is a polymer film containing at least one of a compound represented by formula (1) of hydrates, solvates, or salts thereof. Y is a methine group or nitrogen atom. Q a , Q b , and Q c  are a single bond or a divalent linking group. R a , R b , and R c , are hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, cyano group, halogen group, or heterocyclic group. X 2  is a single bond or a divalent linking group. X 1  is a single bond or a predetermined divalent linking group. R 1  and R 2  are a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, or heterocyclic group Formula (1)

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a divisional application of U.S. patentapplication Ser. No. 14/470,249, filed Aug. 27, 2014, which is adivisional application of U.S. patent application Ser. No. 13/907,357,filed May 31, 2013, which is a continuation of PCT/JP2011/077796 filedon Dec. 1, 2011, and claims priority under 35 U.S.C. §119 to JapanesePatent Application No. 2010/268491, filed on Dec. 1, 2010, JapanesePatent Application No. 2011/066949, filed on Mar. 25, 2011, JapanesePatent Application No. 2011/066950, filed on Mar. 25, 2011, JapanesePatent Application No. 2011/257364, filed on Nov. 25, 2011, and JapanesePatent Application No. 2011/257365, filed on Nov. 25, 2011, the contentof all of which are herein incorporated by reference in their entirety.

TECHNICAL FIELD

The present invention relates to a polymer film that can be used invarious purposes such as a retardation film and a polarizing plateprotective film, and relates to a retardation film, a polarizing plate,and a liquid crystal display that include the polymer film. Theinvention also relates to a novel compound useful in various purposessuch as an additive for the polymer film.

BACKGROUND ART

The display characteristics of a liquid crystal display have beenprogressively improved in recent years. The viewing anglecharacteristics of a liquid crystal display are known to be notablyimproved by a retardation film displaced between a polarizing plate anda liquid crystal cell. For compensation of the viewing angle, it ispreferable to control the optical characteristics of the retardationfilm used, specifically, the in-plane retardation (Re) and/or thicknessdirection retardation (Rth) within appropriate ranges depending on thedisplay mode.

A method disclosed for controlling the Re and Rth of a retardation filminvolves addition of a retardation enhancer to a polymer film (seeJapanese Patent Laid-Open No. 2004-109410). The retardation enhancerdisclosed in this document is a compound capable of forming a molecularcomplex having a keto-enol tautomeric structure as a constituentelement, and a typical example thereof is a compound containing a1,3,5-triazine ring such as a guanamine skeleton. Other retardationenhancers are also disclosed, such as disk-shaped compounds andcompounds having other 1,3,5-triazine ring-containing structures (seeJapanese Patent Laid-Open No. 2001-166144 and Japanese Patent Laid-OpenNo. 2003-344655).

[Patent Literature 1] Japanese Patent Laid-Open No. 2004-109410

[Patent Literature 2] Japanese Patent Laid-Open No. 2001-166144

[Patent Literature 3] Japanese Patent Laid-Open No. 2003-344655

SUMMARY OF INVENTION Technical Problem

The present inventors, who have investigated such conventional polymerfilms containing retardation enhancers, have revealed that the Re andthe Rth significantly vary depending on a change in humidity of theoperating environment (which change may be referred to as humiditydependency of Re and Rth).

It is an object of the present invention to provide a polymer filmhaving reduced variations in Re and Rth caused by a change in humidityof the operating environment and to provide a retardation film, apolarizing plate, and a liquid crystal display that include the polymerfilm.

It is another object of the present invention to provide a novelcompound showing high solution stability and being useful in variouspurposes, such as an additive for polymer films.

Solution to Problem

The present inventors have intensively investigated various compoundsfor usefulness as additives to achieve an effect of enhancing Re andRth. As a result, the inventors have found that a group of compoundseach having a pyrimidine ring or a pyridine ring and having a prescribedsubstituent at a prescribed position on the ring enhances theretardation (Re and/or Rth) of a polymer film and have unexpectedlyfound that in a polymer film containing a compound belonging to thecompound group and thereby having controlled Re and/or Rth, thefluctuations in Re and Rth caused by a change in humidity of theoperating environment are notably reduced compared to those of polymerfilms having controlled Re and/or Rth by conventional retardationenhancers. The present invention was accomplished by furtherinvestigation based on these findings.

The retardation-enhancing function of a compound belonging to thecompound group containing a pyrimidine ring or pyridine ring having aprescribed substituent at a prescribed position, i.e., the function of acompound used in the present invention, differs from the function of theretardation enhancer disclosed in Japanese Patent Laid-Open No.2004-109410 in that the compound of the present invention does not needto forma molecular complex having a triazine ring, and differs from thefunction of the retardation enhancer disclosed in Japanese PatentLaid-Open No. 2001-166144 in that the compound of the present inventiondoes not need to have a disk-like shape. The compound of the presentinvention also differs from the retardation enhancer disclosed in PatentLiterature 3 in that the compound does not contain a 1,3,5-triazinering.

[1] A polymer film comprising at least one kind of compounds representedby Formula (1), hydrates of the compounds, solvates of the compounds,and salts of the compounds:

wherein in Formula (1), Y represents —N— or —C(-Q^(d)-R^(d))—; Q^(a),Q^(b), Q^(c), and Q^(d) each independently represent a single bond or adivalent linking group; R^(a), R^(b), R^(c), and R^(d) eachindependently represent a hydrogen atom, an alkyl group, an alkenylgroup, an alkynyl group, an aryl group, a cyano group, a halogen group,or a heterocyclic group, wherein R^(a) and R^(b) are optionally bondedto each other to form a ring, or R^(a) and R^(d) are optionally bondedto each other to form a ring; X² represents a single bond or a divalentlinking group; X¹ represents a single bond or a divalent group selectedfrom a divalent linking group G¹:

(in each formula, the side indicated by symbol * is a bonding site tothe nitrogen atom introduced into the pyrimidine ring or pyridine ringin the compound represented by the each formula; and R^(g) represents ahydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, anaryl group, or a heterocyclic group); and R¹ and R² each independentlyrepresent a hydrogen atom, an alkyl group, an alkenyl group, an alkynylgroup, an aryl group, or heterocyclic group, wherein R¹ and R² areoptionally bonded to each other to forma ring, provided that compoundsin which only one of -Q^(c)-R^(c) and —N(X¹R¹)X²R² is —NH₂ and compoundsin which Y is a nitrogen atom, both -Q^(c)-R^(c) and —N(X¹R¹)X²R² arenot —NH₂, and -Q^(a)-R^(a) is —NH₂ are excluded.[2] The polymer film according to [1], wherein the at least one kind ofcompounds represented by Formula (1) are added in the form of hydratesof the compounds, solvates of the compounds, or salts of the compounds.[3] wherein Formula (1) is Formula (2):

wherein symbols in Formula (2) are each synonymous with those in Formula(1); X⁴ represents a single bond or a divalent linking group; X³represents a single bond or a divalent group selected from a divalentlinking group G¹:

(in each formula, the side indicated by symbol * is a bonding site tothe nitrogen atom introduced into the pyrimidine ring or pyridine ringin the compound represented by the formula; and R^(g) represents ahydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, anaryl group, or a heterocyclic group); and R³ and R⁴ each independentlyrepresent a hydrogen atom, an alkyl group, an alkenyl group, an alkynylgroup, an aryl group, or a heterocyclic group, wherein R³ and R⁴ areoptionally bonded to each other to form a ring.[4] The polymer film according to [1] or [2], wherein Formula (1) isFormula (3) or (4):

wherein symbols in Formula (3) are each synonymous with those in Formula(1);

wherein symbols in Formula (4) are each synonymous with those in Formula(1).[5] The polymer film according to [1] or [2], wherein Formula (1) isFormula (5-1):

wherein symbols in Formula (5-1) are each synonymous with those inFormula (1); and Ar¹ represents an aryl group.[6] The polymer film according to [1] or [2], wherein Formula (1) isFormula (5-2):

wherein symbols in Formula (5-2) are each synonymous with those inFormulae (1) and (3); and Ar¹ and Ar² each independently represent anaryl group.[7] The polymer film according to [1] or [2], wherein Formula (1) isFormula (6):

wherein symbols in Formula (6) are each synonymous with those in Formula(1); and Ar¹ and Ar² each independently represent an aryl group.[8] The polymer film according to any one of [1] to [7], wherein Q^(a)represents a single bond or —O—, —S—, —NH—, or —N(R)— (wherein R is analkyl group having 1 to 8 carbon atoms); and R^(a) represents a hydrogenatom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms.[9] The polymer film according to [1] or [2], wherein Formula (1) isFormula (7-1):

wherein symbols in Formula (7-1) are each synonymous with those inFormula (1); Q^(aa) represents a single bond or —O—, —S—, —NH—, or—N(R)— (wherein R is an alkyl group having 1 to 8 carbon atoms); R^(aa)represents a hydrogen atom, a halogen atom, or an alkyl group having 1to 8 carbon atoms; R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ each independentlyrepresent a hydrogen atom, a halogen atom, a carbamoyl group, asulfamoyl group, an alkyl group having 1 to 8 carbon atoms, or an alkoxygroup having 1 to 8 carbon atoms.[10] The polymer film according to [1] or [2], wherein Formula (1) isFormula (7-2):

wherein symbols in Formula (7-2) are each synonymous with those inFormula (1); R^(a7) represents an alkyl group having 1 to 8 carbonatoms; and R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ each independently representa hydrogen atom, a halogen atom, a carbamoyl group, a sulfamoyl group,an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1to 8 carbon atoms.[11] The polymer film according to [10], wherein Formula (7-2) isFormula (8), (9), or (10):

wherein symbols in each formula are each synonymous with those inFormula (7-2); and R^(a8), R^(a9), and R^(a10) each independentlyrepresent an alkyl group having 1 to 8 carbon atoms.[12] The polymer film according to [1] or [2], wherein Formula (1) isFormula (11a):

wherein symbols in Formula (11a) are each synonymous with those inFormula (1).[13] The polymer film according to anyone of [1] to [12], furthercomprising at least one kind of compound represented by anyone ofFormulae (IIIe), (IVe), and (Ve) or hydrate of any one of Formulae(IIIe), (IVe), and (Ve), solvate of Formulae (IIIe), (IVe), and (Ve),and salt of any one of Formulae (IIIe), (IVe), and (Ve):

wherein symbols in each formula are each synonymous with those inFormula (1); and Ar's each independently represent an aryl group.[14] A polymer film comprising at least one kind of compoundsrepresented by Formula (I), hydrates of the compounds, solvates of thecompounds, and salts of the compounds:

wherein in Formula (I), Y represents —N— or —C(-Q^(d)-R^(d))—; Q^(a),Q^(b), Q^(c), and Q^(d) each independently represent a single bond or adivalent linking group; R^(a), R^(b), R^(c), and R^(d) eachindependently represent a hydrogen atom, an alkyl group, an alkenylgroup, an alkynyl group, an aryl group, a cyano group, a halogen group,or a heterocyclic group, wherein R^(a) and R^(b) are optionally bondedto each other to form a ring, or R^(a) and R^(d) are optionally bondedto each other to form a ring; X² represents a single bond or a divalentlinking group; X¹ represents a single bond or a divalent group selectedfrom a divalent linking group G¹:

(in each formula, the side indicated by symbol * is a bonding site tothe nitrogen atom introduced into the pyrimidine ring or pyridine ringin the compound represented by the formula; and R^(g) represents ahydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, anaryl group, or a heterocyclic group); and R¹ and R² each independentlyrepresent a hydrogen atom, an alkyl group, an alkenyl group, an alkynylgroup, an aryl group, or a heterocyclic group, wherein R¹ and R² areoptionally bonded to each other to form a ring, provided that one of-Q^(c)-R^(c) and N(X¹R¹)X²R² is —NH₂ and both are not simultaneously—NH₂ and that when Y is a nitrogen atom and when N(X¹R¹)X²R² is —NH₂,-Q^(a)-R^(a) is not —NH₂.[15] The polymer film according to [14], wherein Formula (I) is Formula(II):

wherein symbols in Formula (II) are each synonymous with those inFormula (I); Y represents —N— or —C(-Q^(d)-R^(d))—, and Z represents —N—or —C(-Q^(b)-R^(b))—, provided that Y and Z are not simultaneously —N—;X¹ represents a single bond or a linking group selected from the groupconsisting of divalent linking groups represented by a divalent linkinggroup G²; X² represents a single bond or a divalent linking group; R¹and R² each independently represent a hydrogen atom, an alkyl group, analkenyl group, an alkynyl group, an aryl group, or a heterocycle, and atleast one of —X¹—R¹ and —X²—R² is a substituent other than a hydrogenatom; Q^(a), Q^(b), and Q^(d) each independently represent a single bondor —O—, —S—, or —NR′—, wherein R′ represents a hydrogen atom, an alkylgroup, an alkenyl group, an alkynyl group, an aryl group, or aheterocycle, and Q^(a) and R^(a), Q^(d) and R^(d), or Q^(b) and R^(b)are optionally bonded to each other to form a ring, or-Q^(a)-R^(a)—R^(d)-Q^(d)- or -Q^(a)-R^(a)—R^(b)-Q^(b) optionally forms aring; and R^(a) represents a hydrogen atom, a halogen, an alkyl group,an alkenyl group, an alkynyl group, an aryl group, or a heterocycle,provided that when Z is —N—, -Q^(a)-R^(a) represents a substituent otherthan an amino group and that R^(b) and R^(d) each independentlyrepresent a hydrogen atom, an alkyl group, an alkenyl group, an alkynylgroup, an aryl group, or a heterocycle;

wherein symbols in the divalent linking group G² are each synonymouswith those in the divalent linking group G¹.[16] The polymer film according to [15], wherein Formula (II) is Formula(III), Formula (IV), or Formula (V):

wherein symbols in Formula (III) are each synonymous with those inFormula (II);

wherein symbols in Formula (IV) are each synonymous with those inFormula (II);

wherein symbols in Formula (V) are each synonymous with those in Formula(II).[17] The polymer film according to [15], wherein Formula (II) is Formula(IIIa), (IVa), or (Va):

wherein symbols in Formula (IIIa) are each synonymous with those inFormula (II);

wherein symbols in Formula (IVa) are each synonymous with those inFormula (II);

wherein symbols in Formula (Va) are each synonymous with those inFormula (II).[18] The polymer film according to [15], wherein Formula (II) is Formula(IIIb), Formula (IVb), or Formula (Vb):

wherein symbols in Formula (IIIb) are each synonymous with those inFormula (II);

wherein symbols in Formula (IVb) are each synonymous with those inFormula (II);

wherein symbols in Formula (Vb) are each synonymous with those inFormula (II).[19] The polymer film according to [15], wherein Formula (II) is Formula(IIIc), Formula (IVc), or Formula (Vc):

wherein symbols in Formula (IIIc) are each synonymous with those inFormula (II); and R⁹ represents —O—Ar, an alkyl group, an alkenyl group,an alkynyl group, an aryl group, or a heterocyclic group, wherein Arrepresents an aryl group;

wherein symbols in Formula (IVc) are each synonymous with those inFormula (II); and R⁹ represents —O—Ar, an alkyl group, an alkenyl group,an alkynyl group, an aryl group, or a heterocyclic group, wherein Arrepresents an aryl group;

wherein symbols in Formula (Vc) are each synonymous with those inFormula (II); and R⁹ represents —O—Ar, an alkyl group, an alkenyl group,an alkynyl group, an aryl group, or a heterocyclic group, and Arrepresents an aryl group.[20] The polymer film according to [15], wherein Formula (II) is Formula(IIId), Formula (IVd), or Formula (Vd):

wherein symbols in Formula (IIId) are each synonymous with those inFormula (II);

wherein symbols in Formula (IVd) are each synonymous with those inFormula (II);

wherein symbols in Formula (Vd) are each synonymous with those inFormula (II).[21] The polymer film according to [15], wherein Formula (II) is Formula(IIIe), (IVe), or (Ve):

wherein symbols in Formula (IIIe) are each synonymous with those inFormula (II); and Ar represents an aryl group;

wherein symbols in Formula (IVe) are each synonymous with those inFormula (II); and Ar represents an aryl group;

wherein symbols in Formula (Ve) are each synonymous with those inFormula (II); and Ar represents an aryl group.[22] The polymer film according to any one of [14] to [21], whereinQ^(a) represents a single bond or —O—, —NH—, or —N(R)— (wherein R is analkyl group having 1 to 8 carbon atoms); and R^(a) represents a hydrogenatom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms.[23] The polymer film according to [15], wherein Formula (II) is Formula(IIIf), (IIIg), (IIIh), (IVf), (IVg), (IVh), or (Vf):

wherein in Formula (IIIf), R^(a7) represents an alkyl group having 1 to8 carbon atoms; and R⁶, R⁷ and R⁸ each independently represent ahydrogen atom, a halogen atom, a nitro group, a cyano group, a carbamoylgroup, an N-alkylcarbamoyl group having 1 to 8 carbon atoms, anN,N-dialkylcarbamoyl group having 1 to 16 carbon atoms, a sulfamoylgroup, an N-alkylsulfamoyl group having 1 to 8 carbon atoms, anN,N-dialkylsulfamoyl group having 1 to 16 carbon atoms, an alkyl grouphaving 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbonatoms, an alkylamino group having 1 to 16 carbon atoms, a dialkylaminogroup having 1 to 16 carbon atoms, or an alkoxyalkyloxy group having 1to 16 carbon atoms;

wherein symbols in Formula (IIIg) are each synonymous with those inFormula (IIIf);

wherein symbols in Formula (IIIh) are each synonymous with those inFormula (IIIf);

wherein symbols in Formula (IVf) are each synonymous with those inFormula (IIIf);

wherein symbols in Formula (IVg) are each synonymous with those inFormula (IIIf);

wherein symbols in Formula (IVh) are each synonymous with those inFormula (IIIf);

wherein symbols in Formula (Vf) are each synonymous with those inFormula (IIIf).[24] The polymer film according to any one of [14] to [23], wherein atleast one kind of the compounds are added in the form of hydrates of thecompounds, solvates of the compounds, or salts of the compounds.[25] The polymer film according to anyone of [1] to [24], comprising ahydroxyl group-containing polymer as a main component.[26] The polymer film according to [25], wherein the hydroxylgroup-containing polymer is a cellulose acylate resin.[27] The polymer film according to [26], wherein the cellulose acylateresin is a cellulose acetate resin.[28] The polymer film according to anyone of [1] to [27], being formedby a solution-casting method.[29] The polymer film according to [28], wherein the hydrates of thecompounds or solvate of the compounds is used.[30] A retardation film consisting of the polymer film according to anyone of [1] to [29] or comprising the polymer film according to any oneof [1] to [29].[31] A polarizing plate comprising a polarizer and the polymer filmaccording to any one of [1] to [29].[32] A liquid crystal display comprising the polymer film according toany one of [1] to [29] and/or the polarizing plate according to [31].[33] A compound represented by Formula (7-1) or a hydrate of thecompound, a solvate of the compound, or a salt of the compound:

wherein in Formula (7-1), Y represents —N— or —C(-Q^(d)-R^(d))—, Q^(d)represents a single bond or a divalent linking group, and R^(d)represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynylgroup, an aryl group, a cyano group, a halogen group, or a heterocyclicgroup; Q^(aa) represents a single bond or —O—, —S—, —NH—, or —N(R)—(wherein R is an alkyl group having 1 to 8 carbon atoms); R^(aa)represents a hydrogen atom, a halogen atom, or an alkyl group having 1to 8 carbon atoms, and R^(d) and R^(aa) are optionally bonded to eachother to form a ring structure; and R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶each independently represent a hydrogen atom, a halogen atom, acarbamoyl group, a sulfamoyl group, an alkyl group having 1 to 8 carbonatoms, or an alkoxy group having 1 to 8 carbon atoms.[34] A compound represented by Formula (7-2) or a hydrate of thecompound, a solvate of the compound, or a salt of the compound:

wherein in Formula (7-2), Y represents —N— or —C(-Q^(d)-R^(d))—, Q^(d)represents a single bond or a divalent linking group, and R^(d)represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynylgroup, an aryl group, a cyano group, a halogen group, or a heterocyclicgroup; Q^(a) represents a single bond or a divalent linking group;R^(a7) represents an alkyl group having 1 to 8 carbon atoms, and R^(d)and R^(a7) are optionally bonded to each other to form a ring; and R¹¹,R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ each independently represent a hydrogenatom, a halogen atom, a carbamoyl group, a sulfamoyl group, an alkylgroup having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8carbon atoms.[35] The compound or a hydrate of the compound, a solvate of thecompound, or a salt of the compound according to [33] or [34], thecompound being represented by Formula (8), Formula (9), or Formula (10):

wherein R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ each independently represent ahydrogen atom, a halogen atom, a carbamoyl group, a sulfamoyl group, analkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8carbon atoms; and R^(a8), R^(a9), and R^(a10) each independentlyrepresent an alkyl group having 1 to 8 carbon atoms.[36] The compound or a hydrate of the compound, a solvate of thecompound, or a salt of the compound according to [35], R^(a8), R^(a9),and R^(a10) each independently represent an alkyl group having 1 to 4carbon atoms.[37] A compound represented by Formula (IIIc), Formula (IVc), or Formula(Vf′) or a hydrate of the compound, a solvate of the compound, or a saltof the compound:

wherein in Formula (IIIc), Q^(a) represents a single bond or a divalentlinking group; R^(a) represents a hydrogen atom, an alkyl group, analkenyl group, an alkynyl group, an aryl group, a cyano group, a halogengroup, or a heterocyclic group; and R⁹ represents —O—Ar, an alkyl group,an alkenyl group, an alkynyl group, an aryl group, or a heterocyclicgroup, wherein Ar represents an aryl group;

wherein symbols in Formula (IVc) are each synonymous with those inFormula (IIIc);

wherein R¹¹, R¹², and R¹³ each independently represent a hydrogen atom,a nitro group, a carbamoyl group, an N-alkylcarbamoyl group having 1 to8 carbon atoms, an N,N-dialkylcarbamoyl group having 1 to 16 carbonatoms, a sulfamoyl group, an N-alkylsulfamoyl group having 1 to 8 carbonatoms, an N,N-dialkylsulfamoyl group having 1 to 16 carbon atoms, analkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16carbon atoms, an alkylamino group having 1 to 16 carbon atoms, adialkylamino group having 1 to 16 carbon atoms, or an alkoxyalkyloxygroup having 1 to 16 carbon atoms, provided that at least one of R¹¹,R¹², and R¹³ represents a substituent other than a hydrogen atom.[38] The compound or a hydrate of the compound, a solvate of thecompound, or a salt of the compound according to [37], wherein Q^(a)represents a single bond or —O—, —NH—, or —N(R)— (wherein R is an alkylgroup having 1 to 8 carbon atoms); and R^(a) represents a hydrogen atom,a halogen atom, or an alkyl group having 1 to 8 carbon atoms.[39] A compound represented by Formula (IIIf), Formula (IIIg), Formula(IIIh), Formula (IVf), Formula (IVg), or Formula (IVh) or a hydrate ofthe compound, a solvate of the compound, or a salt of the compound:

wherein in Formula (IIIf), R^(a7) represents an alkyl group having 1 to8 carbon atoms; and R⁶, R⁷, and R⁸ each independently represent ahydrogen atom, a halogen atom, a nitro group, a cyano group, a carbamoylgroup, an N-alkylcarbamoyl group having 1 to 8 carbon atoms, anN,N-dialkylcarbamoyl group having 1 to 16 carbon atoms, a sulfamoylgroup, an N-alkylsulfamoyl group having 1 to 8 carbon atoms, anN,N-dialkylsulfamoyl group having 1 to 16 carbon atoms, an alkyl grouphaving 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbonatoms, an alkylamino group having 1 to 16 carbon atoms, a dialkylaminogroup having 1 to 16 carbon atoms, or an alkoxyalkyloxy group having 1to 16 carbon atoms;

wherein symbols in Formula (IIIg) are each synonymous with those inFormula (IIIf);

wherein symbols in Formula (IIIh) are each synonymous with those inFormula (IIIf);

wherein symbols in Formula (IVf) are each synonymous with those inFormula (IIIf);

wherein symbols in Formula (IVg) are each synonymous with those inFormula (IIIf);

wherein symbols in Formula (IVg) are each synonymous with those inFormula (IIIf).[40] A hydrate of the compound or a solvate of the compound according toany one of [33] to [39].[41] A hydrate of the compound according to any one of [33] to [39].[42] A method of producing a compound represented by Formula (7-1) or asalt of the compound, a hydrate of the compound, or a solvate of thecompound, which comprises

reacting with a compound represented by Formula (7a), a compoundrepresented by a scheme, and represented by Formula (7b):

wherein in Formula (7a) and Formula (7b), Q^(aa) represents a singlebond or —O—, —S—, —NH—, or —N(R)— (wherein R is an alkyl group having 1to 8 carbon atoms); R^(aa) represents a hydrogen atom, a halogen atom,or an alkyl group having 1 to 8 carbon atoms; R¹⁴, R¹⁵, and R¹⁶ eachindependently represent a hydrogen atom, a halogen atom, a carbamoylgroup, a sulfamoyl group, an alkyl group having 1 to 8 carbon atoms, oran alkoxy group having 1 to 8 carbon atoms; and Z represents a halogenatom, a hydroxy group, an alkoxy group, aryloxy group, or an acyloxygroup.[43] The method according to [42], further comprising:

crystallizing the compound represented by Formula (7-2) from water or anorganic solvent to yield the hydrate of the compound represented byFormula (7-1) or solvate of the compound.

Advantageous Effects of Invention

The present invention can provide a polymer film showing reducedfluctuations in Re and Rth caused by a change in humidity of theoperating environment and a retardation film, a polarizing plate, and aliquid crystal display that include the polymer film.

The invention can also provide a novel compound showing high solutionstability and being useful in various purposes, such as an additive forpolymer films.

BRIEF DESCRIPTION OF DRAWING

FIG. 1 is a schematic diagram showing the structure of an example liquidcrystal display of the present invention.

DESCRIPTION OF EMBODIMENTS

The present invention will now be described in detail. The constituentrequirement described below may be based on a typical embodiment of thepresent invention; however, the present invention should not be limitedthereto. Throughout the specification, a numerical range defined with“to” is meant to include the numbers preceding and following the “to” asthe lower limit and the upper limit, respectively.

Terms used in the specification will now be described.

(Retardation (Re and Rth))

In this description, Re (λ) and Rth (λ) are retardation (nm) in planeand retardation (nm) along the thickness direction, respectively, at awavelength of λ. Re(λ) is measured by applying light having a wavelengthof λ nm to a film in the normal direction of the film, using KOBRA 21ADHor WR (by Oji Scientific Instruments). The selection of the measurementwavelength may be conducted according to the manual-exchange of thewavelength-selective-filter or according to the exchange of themeasurement value by the program.

When a film to be analyzed is expressed by a monoaxial or biaxial indexellipsoid, Rth(λ) of the film is calculated as follows.

Rth (λ) is calculated by KOBRA 21ADH or WR on the basis of the six Re(λ)values which are measured for incoming light of a wavelength λ nm in sixdirections which are decided by a 10° step rotation from 0° to 50° withrespect to the normal direction of a sample film using an in-plane slowaxis, which is decided by KOBRA 21ADH, as an inclination axis (arotation axis; defined in an arbitrary in-plane direction if the filmhas no slow axis in plane), a value of hypothetical mean refractiveindex, and a value entered as a thickness value of the film.

In the above, when the film to be analyzed has a direction in which theretardation value is zero at a certain inclination angle, around thein-plane slow axis from the normal direction as the rotation axis, thenthe retardation value at the inclination angle larger than theinclination angle to give a zero retardation is changed to negativedata, and then the Rth(λ) of the film is calculated by KOBRA 21ADH orWR.

Around the slow axis as the inclination angle (rotation angle) of thefilm (when the film does not have a slow axis, then its rotation axismay be in any in-plane direction of the film), the retardation valuesare measured in any desired inclined two directions, and based on thedata, and the estimated value of the mean refractive index and theinputted film thickness value, Rth may be calculated according toformulae (X) and (XI):

(X)

$\begin{matrix}{{{Re}(\theta)} = {\quad{\left\lbrack {{nx} - \frac{{ny} \times {nz}}{\sqrt{\begin{matrix}{\left( {{ny}\mspace{11mu} {\sin \left( {\sin^{- 1}\left( \frac{\sin \left( {- \theta} \right)}{nx} \right)} \right)}} \right)^{2} +} \\\left( {{nz}\mspace{11mu} {\cos \left( {\sin^{- 1}\left( \frac{\sin \left( {- \theta} \right)}{nx} \right)} \right)}} \right)^{2}\end{matrix}}}} \right\rbrack \times \frac{d}{\cos \left( {\sin^{- 1}\left( \frac{\sin \left( {- \theta} \right)}{nx} \right)} \right)}}}} & \left\lbrack {{Math}.\mspace{14mu} 1} \right\rbrack\end{matrix}$

Re(θ) represents a retardation value in the direction inclined by anangle θ from the normal direction; nx represents a refractive index inthe in-plane slow axis direction; ny represents a refractive index inthe in-plane direction perpendicular to nx; and nz represents arefractive index in the direction perpendicular to nx and ny. And “d” isa thickness of the film.

Rth={(nx+ny)/2−nz}×d  (XI):

In the formula, nx represents a refractive index in the in-plane slowaxis direction; ny represents a refractive index in the in-planedirection perpendicular to nx; and nz represents a refractive index inthe direction perpendicular to nx and ny. And “d” is a thickness of thefilm.

When the film to be analyzed is not expressed by a monoaxial or biaxialindex ellipsoid, or that is, when the film does not have an opticalaxis, then Rth(λ) of the film may be calculated as follows:

Re(λ) of the film is measured around the slow axis (judged by KOBRA21ADH or WR) as the in-plane inclination axis (rotation axis), relativeto the normal direction of the film from −50 degrees up to +50 degreesat intervals of 10 degrees, in 11 points in all with a light having awavelength of λ nm applied in the inclined direction; and based on thethus-measured retardation values, the estimated value of the meanrefractive index and the inputted film thickness value, Rth(λ) of thefilm may be calculated by KOBRA 21ADH or WR.

In the above-described measurement, the hypothetical value of meanrefractive index is available from values listed in catalogues ofvarious optical films in Polymer Handbook (John Wiley & Sons, Inc.).Those having the mean refractive indices unknown can be measured usingan Abbe refract meter. Mean refractive indices of some main opticalfilms are listed below:

-   -   cellulose acylate (1.48), cycloolefin polymer (1.52),        polycarbonate (1.59), polymethylmethacrylate (1.49) and        polystyrene (1.59). KOBRA 21ADH or WR calculates nx, ny and nz,        upon enter of the hypothetical values of these mean refractive        indices and the film thickness. On the basis of thus-calculated        nx, ny and nz, Nz=(nx-nz)/(nx-ny) is further calculated.

In the present invention, the “slow axis” of, for example, a retardationfilm represents the direction showing a maximum refractive index. Theterm “visible light region” covers 380 to 780 nm. The refractive indexis measured at a wavelength λ of 589 nm in a visible light region,unless specifically mentioned.

Throughout the specification, numerical values, numerical ranges, andqualitative expressions (expressions such as “equivalent” and “equal”)showing the optical characteristics of each component such as aretardation film and a liquid crystal layer are interpreted to benumerical values, numerical ranges, and characteristics including errorsgenerally acceptable for liquid crystal displays and components thereof.

1. Polymer Film

The polymer film of the present invention contains at least one kind ofthe compounds represented by Formula (0) shown below, hydrates of thecompounds, solvates of the compounds, and salts of the compounds. Thecompound represented by Formula (0) or a hydrate of the compound,solvate of the compound, or salt of the compound functions as aretardation enhancer, and the polymer film containing such a compoundhas higher Re and/or Rth compared to a polymer film produced by the samematerials and the same process except that the compound is notcontained. In addition, the variation in at least one of the Re and Rthcaused by a change in humidity of the operating environment is reducedin the polymer film having controlled Re and/or Rth by a compoundrepresented by Formula (0) or a hydrate of the compound, solvate of thecompound, or salt of the compound, compared to the polymer film havingcontrolled Re and/or Rth by any other retardation enhancer (e.g.,disk-shaped compound having a triazine ring as the central core).

Furthermore, in an embodiment of producing a polymer film by a liquidfilm forming process, i.e., formation of a polymer film from a dopeprepared by dissolving a polymer material (which is a term includingboth resin and polymer) as a main component and a component representedby Formula (0) in an organic solvent, the compound represented byFormula (0) is preferably in a hydrate, solvate, or salt form, morepreferably in a hydrate or solvate form, from the viewpoint of qualitystabilization of the produced film.

Various materials and methods that can be used for producing the polymerfilm of the present invention will now be described in detail.

(1-1) Compound represented by Formula (0) or hydrate of the compound,solvate of the compound, or salt of the compound.

The polymer film of the present invention contains at least one ofcompounds represented by Formula (0) shown below and hydrates of thecompounds, solvates of the compounds, and salts of the compounds(hereinafter, may be referred to as “inventive compound”). The compoundrepresented by Formula (0) or a hydrate of the compound, solvate of thecompound, or a salt of the compound has an enhancing effect on the Reand/or Rth of a polymer film, in other words, the compound functions asa retardation enhancer. A polymer film containing a hydrophilic polymer,in particular, a hydroxyl group-containing polymer, as a main componenttends to increase the fluctuations in Re and Rth caused by a change inhumidity of operating environment. The compound represented by Formula(0) or a hydrate of the compound, solvate of the compound, or salt ofthe compound has a function of reducing at least one of the fluctuationsin Re and Rth caused by a change in humidity of operating environment,in other words, the compound also functions as a humidity-dependencyreducer for polymer films.

In the present invention, the “humidity-dependency reducer for polymerfilm” is an agent that can reduce the fluctuations in Re and/or Rth of apolymer film containing the agent, where the fluctuations depend on themoisture of the polymer film. Specifically, an agent-free polymer filmto be tested and an agent-containing polymer film are prepared; the Reand the Rth (also referred to as Re [25° C., RH10%] and Rth [25° C.,RH10%], respectively) of these polymer films humidified at a relativehumidity of 10% at 25° C. for 12 hours and the Re and the Rth (alsoreferred to as Re [25° C., RH80%] and Rth [25° C., RH80%], respectively)of the polymer films humidified at a relative humidity of 80% at 25° C.for 12 hours are measured and compared to each other. If the fluctuationin the Re and/or Rth of the agent-containing polymer film is smallerthan that of the agent-free polymer film, the agent is termed ahumidity-dependency reducer.

In addition, the compound represented by Formula (0) or a hydrate of thecompound, solvate of the compound, or salt of the compound is highlystable in a state dissolved in an organic solvent. Accordingly, use ofsuch a compound contributes to an improvement in stability in productionof a polymer film, in particular, production by a solution-castingmethod.

Throughout the specification, the terms “alkyl group”, “alkenyl group”,and “alkynyl group” each include both linear and branched groups.

In Formula (0), Y represents —N— or —C(-Q^(d)-R^(d))—; Q^(a), Q^(b),Q^(c), and Q^(d) each independently represent a single bond or adivalent linking group; R^(a), R^(b), R^(c), and R^(d) eachindependently represent a hydrogen atom, an alkyl group, an alkenylgroup, an alkynyl group, an aryl group, a cyano group, a halogen group,or a heterocyclic group, wherein R^(a) and R^(b) are optionally bondedto each other to form a ring, or R^(a) and R^(d) are optionally bondedto each other to form a ring; X² represents a single bond or a divalentlinking group; X¹ represents a single bond or a divalent group selectedfrom a divalent linking group G¹ shown below; and R¹ and R² eachindependently represent a hydrogen atom, an alkyl group, an alkenylgroup, an alkynyl group, an aryl group, or a heterocyclic group, whereinR¹ and R² are optionally bonded to each other to form a ring.

The compounds represented by Formula (0) are classified into a compoundgroup A and a compound group B. The compound group A excludes compoundsin which only one of -Q^(c)-R^(c) and —N(X¹R¹)X²R² is —NH₂ and compoundsin which Y is a nitrogen atom, both -Q^(c)-R^(c) and —N(X¹R¹)X²R² arenot —NH₂, and -Q^(a)-R^(a) is —NH₂, i.e., excludes monoamines having thepartial structures shown below; and the compound group B includesmonoamines having the partial structures shown below. Compoundsbelonging to the compound group A and the compound group B will now beseparately described.

In the formulae, the symbol * each denotes a position to which any oneof Q^(a)-R^(a), -Q^(b)-R^(b), -Q^(c)-R^(c), -Q^(d)-R^(d), and—N(X¹R¹)X²R² bonds and represents a substituent other than NH₂.(1a-1) the Compound Group A

Compounds belonging to the compound group A are represented by Formula(1) and are preferably represented by Formula (2).

In Formula (1), Y represents —N— or —C(-Q^(d)-R^(d))—; Q^(a), Q^(b),Q^(c), and Q^(d) each independently represent a single bond or adivalent linking group; R^(a), R^(b) and R^(d) each independentlyrepresent a hydrogen atom, an alkyl group, an alkenyl group, an alkynylgroup, an aryl group, a cyano group, a halogen group, or a heterocyclicgroup, wherein R^(a) and R^(b) are optionally bonded to each other toform a ring, R^(a) and R^(d) are optionally bonded to each other to forma ring; X² represents a single bond or a divalent linking group; X¹represents a single bond or a divalent group selected from the divalentlinking group G¹ shown below; and R¹ and R² each independently representa hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, anaryl group, or a heterocyclic group, wherein R¹ and R² are optionallybonded to each other to form a ring.

In the compounds mentioned above, compounds in which only one of-Q^(c)-R^(c) and —N(X¹R¹)X²R² is —NH₂ and compounds in which Y is anitrogen atom, both -Q^(c)-R^(c) and —N(X¹R¹) X²R² are not —NH₂, and-Q^(a)-R^(a) is —NH₂ are excluded, that is, monoamines having thepartial structures shown below are excluded.

In the formulae, the symbol * each denotes a position to which any oneof -Q^(a)-R^(a), -Q^(b)-R^(b), -Q^(c)-R^(c), -Q^(d)-R^(d), and—N(X¹R¹)X²R² bonds and represents a substituent other than NH₂.

Symbols in Formula (2) are each synonymous with those in Formula (1); X⁴represents a single bond or a divalent linking group; X³ represents asingle bond or a divalent group selected from the divalent linking groupG¹ shown below; and R³ and R⁴ each independently represent a hydrogenatom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group,or a heterocyclic group, wherein R³ and R⁴ are optionally bonded to eachother to forma ring, provided that compounds in which only one of—N(X³R³) X⁴R⁴ and —N(X¹R¹)X²R² is —NH₂ and compounds in which Y is anitrogen atom, both -Q^(c)-R^(c) and —N(X¹R¹)X²R² are not —NH₂, and-Q^(a)-R^(a) is —NH₂ are excluded.

In Formulae (1) and (2), the 6-membered ring is a pyridine ring when Yrepresents —C(-Q^(d)-R^(d))— and is a pyrimidine ring when Y represents—N—.

In Formulae (1) and (2), examples of the each divalent linking grouprepresented by Q^(a), Q^(b), Q^(c), or Q^(d) include —O—, —S—,—N(X^(a)—R^(h))—, and —N(X^(a)—R^(h))—X^(h)—. Herein, X^(a) and X^(b)each independently represent a single bond or a divalent linking group.Examples of the divalent liner represented by X^(a) or X^(b) include—CO—, —COO—, and —CONH—. R^(h) represents a hydrogen atom, an alkylgroup having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbonatoms, an alkynyl group having 2 to 8 carbon atoms, an aryl group having6 to 10 carbon atoms, or a heterocyclic group having 2 to 10 carbonatoms. Preferred examples of the each divalent linking group representedby Q^(a), Q^(b), Q^(c) or Q^(d) include single bonds, —O—, —S—,—N(X^(a)—R^(h))—, and —N(X^(a)—R^(h))—X^(b)—; and the divalent linkinggroup is more preferably a single bond, —O—, —N(X^(a)—R^(h))—, or—N(X^(a)—R^(h))—X^(b)—, and most preferably a single bond, —O—, —NH—, or—NH—X^(b)—. Preferred examples of —NH—X^(b)— include —NH—CO—, —NH—COO—,—NH—CONH—, and —NH—SO₂—; and —NH—X^(b)— is more preferably —NH—CO— or—NH—COO—. Q^(d) preferably represents a single bond.

In Formulae (1) and (2), R^(a), R^(b), R^(c), and R^(d) eachindependently represent a hydrogen atom, an alkyl group, an alkenylgroup, an alkynyl group, an aryl group, a cyano group, a halogen group,or a heterocyclic group, wherein R^(a) and R^(b) are optionally bondedto each other to form a ring, or R^(a) and R^(d) are optionally bondedto each other to form a ring.

When R^(a), R^(b), R^(c), or R^(d) each represents the alkyl group, thealkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 8carbon atoms, and most preferably 1 to 4 carbon atoms. When R^(a),R^(b), R^(c), or R^(d) each represents the alkyl group, one carbon atomor non-adjacent two or more carbon atoms are each optionally replaced bya hetero atom selected from oxygen, sulfur, and nitrogen atoms(including —NH— and —N(R)— (R: alkyl group)). For example, R^(a), R^(b),R^(c), and R^(d) may each be an alkylene (e.g., ethylene or propylene)oxy group.

When R^(a), R^(b), R^(c), or R^(d) each represents the alkenyl group,the alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2to 8 carbon atoms, and most preferably 2 to 4 carbon atoms.

When R^(a), R^(b), R^(c), or R^(d) each represents the alkynyl group,the alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2to 8 carbon atoms, and most preferably 2 to 4 carbon atoms.

When R^(a), R^(b), R^(c), or R^(d) each represents the aryl group, thearyl group preferably has 6 to 24 carbon atoms, more preferably 6 to 18carbon atoms, and most preferably 6 to 10 carbon atoms, from theviewpoint of reducing humidity dependency. Specifically, the aryl groupis preferably a benzene ring or a naphthalene ring and most preferably abenzene ring.

When R^(a), R^(b), R^(c), or R^(d) each represents the heterocyclicgroup, the heterocyclic group preferably has 4 to 20 carbon atoms, morepreferably 4 to 10 carbon atoms, and most preferably 4 to 6 carbonatoms, from the viewpoint of reducing humidity dependency. Specificexamples of the heterocyclic group include pyrrolyl group, pyrrolidinogroup, pyrazolyl group, pyrazolidino group, imidazolyl group, piperazinogroup, and morpholino group.

R^(a) and R^(b), and R^(a) and R^(d) are optionally bonded to each otherto form a ring. The ring to be formed may be a hydrocarbon ring or aheterocycle and is preferably a 5-membered or 6-membered ring.

R^(a), R^(b), R^(c), and R^(d) each optionally further have one or moresubstituents, if possible. Examples of the substituent optionallypossessed by R^(a), R^(b), R^(c), or R^(d) include the followingsubstituent group T.

Substituent Group T:

Alkyl groups (those preferably having 1 to 20 carbon atoms, morepreferably 1 to 12 carbon atoms, and most preferably 1 to 8 carbonatoms, and examples thereof include methyl group, ethyl group, isopropylgroup, tert-butyl group, n-octyl group, n-decyl group, n-hexadecylgroup, cyclopropyl group, cyclopentyl group, and cyclohexyl group);alkenyl groups (those preferably having 2 to 20 carbon atoms, morepreferably 2 to 12 carbon atoms, and most preferably 2 to 8 carbonatoms, and examples thereof include vinyl group, allyl group, 2-butenylgroup, and 3-pentenyl group), alkynyl groups (those preferably having 2to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and mostpreferably 2 to 8 carbon atoms, and examples thereof include propargylgroup and 3-pentynyl group), aryl groups (those preferably having 6 to30 carbon atoms, more preferably 6 to 20 carbon atoms, and mostpreferably 6 to 12 carbon atoms, and examples thereof include phenylgroup, biphenyl group, and naphthyl group), amino groups (thosepreferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbonatoms, and most preferably 0 to 6 carbon atoms, and examples thereofinclude amino group, methylamino group, dimethylamino group,diethylamino group, and dibenzylamino group), alkoxy group (thosepreferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbonatoms, and most preferably 1 to 8 carbon atoms, and examples thereofinclude methoxy group, ethoxy group, and butoxy group), aryloxy groups(those preferably having 6 to 20 carbon atoms, more preferably 6 to 16carbon atoms, and most preferably 6 to 12 carbon atoms, and examplesthereof include phenyloxy group and 2-naphthyloxy group), acyl groups(those preferably having 1 to 20 carbon atoms, more preferably 1 to 16carbon atoms, and most preferably 1 to 12 carbon atoms, and examplesthereof include acetyl group, benzoyl group, formyl group, and pivaloylgroup), alkoxycarbonyl groups (those preferably having 2 to 20 carbonatoms, more preferably 2 to 16 carbon atoms, and most preferably 2 to 12carbon atoms, and examples thereof include methoxycarbonyl group andethoxycarbonyl group), aryloxycarbonyl groups (those preferably having 7to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and mostpreferably 7 to 10 carbon atoms, and examples thereof includephenyloxycarbonyl group), acyloxy groups (those preferably having 2 to20 carbon atoms, more preferably 2 to 16 carbon atoms, and mostpreferably 2 to 10 carbon atoms, and examples thereof include acetoxygroup and benzoyloxy group), acylamino groups (those preferably having 2to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and mostpreferably 2 to 10 carbon atoms, and examples thereof includeacetylamino group and benzoylamino group), alkoxycarbonylamino groups(those preferably having 2 to 20 carbon atoms, more preferably 2 to 16carbon atoms, and most preferably 2 to 12 carbon atoms, and examplesthereof include methoxycarbonylamino group), aryloxycarbonylamino groups(those preferably having 7 to 20 carbon atoms, more preferably 7 to 16carbon atoms, and most preferably 7 to 12 carbon atoms, and examplesthereof include phenyloxycarbonylamino group), sulfonylamino groups(those preferably having 1 to 20 carbon atoms, more preferably 1 to 16carbon atoms, and most preferably 1 to 12 carbon atoms, and examplesthereof include methanesulfonylamino group and benzenesulfonylaminogroup), sulfamoyl groups (those preferably having 0 to 20 carbon atoms,more preferably 0 to 16 carbon atoms, and most preferably 0 to 12 carbonatoms, and examples thereof include sulfamoyl group, methylsulfamoylgroup, dimethylsulfamoyl group, and phenylsulfamoyl group), carbamoylgroups (those preferably having 1 to 20 carbon atoms, more preferably 1to 16 carbon atoms, and most preferably 1 to 12 carbon atoms, andexamples thereof include carbamoyl group, methylcarbamoyl group,diethylcarbamoyl group, and phenylcarbamoyl group), alkylthio groups(those preferably having 1 to 20 carbon atoms, more preferably 1 to 16carbon atoms, and most preferably 1 to 12 carbon atoms, and examplesthereof include methylthio group and ethylthio group), arylthio groups(those preferably having 6 to 20 carbon atoms, more preferably 6 to 16carbon atoms, and most preferably 6 to 12 carbon atoms, and examplesthereof include phenylthio group), sulfonyl groups (those preferablyhaving 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, andmost preferably 1 to 12 carbon atoms, and examples thereof include mesylgroup and tosyl group), sulfinyl groups (those preferably having 1 to 20carbon atoms, more preferably 1 to 16 carbon atoms, and most preferably1 to 12 carbon atoms, and examples thereof include methanesulfinyl groupand benzenesulfinyl group), ureido groups (those preferably having 1 to20 carbon atoms, more preferably 1 to 16 carbon atoms, and mostpreferably 1 to 12 carbon atoms, and examples thereof include ureidogroup, methylureido group, and phenylureido group), phosphoric amidogroups (those preferably having 1 to 20 carbon atoms, more preferably 1to 16 carbon atoms, and most preferably 1 to 12 carbon atoms, andexamples thereof include diethylphosphoric amide and phenylphosphoricamide), a hydroxyl group, a mercapto group, halogen atoms (e.g.,fluorine atom, chlorine atom, bromine atom, and iodine atom), a cyanogroup, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acidgroup, a sulfino group, a hydrazino group, an imino group, heterocycles(those preferably having 1 to 30 carbon atoms and more preferably 1 to12 carbon atoms, examples of the hetero atom include nitrogen atom,oxygen atom, sulfur atom, and specific examples of the heterocycleinclude imidazolyl group, pyridyl group, quinolyl group, furyl group,piperidyl group, morpholino group, benzoxazolyl group, benzimidazolylgroup, and benzthiazolyl group), and silyl groups (those preferablyhaving 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, andmost preferably 3 to 24 carbon atoms, and examples thereof includetrimethylsilyl group and triphenylsilyl group).

These substituents may further have substituents. When the substituentbelonging to the substituent group T has two or more substituents, thesubstituents may be the same or different and may be bonded to eachother to form a ring, if possible.

In Formulae (1) and (2), R^(a) and R^(b) are each preferably a hydrogenatom or a substituted or unsubstituted alkyl group. In Formula (1),R^(c) is preferably a hydrogen atom, a substituted or unsubstitutedalkyl group, a substituted or unsubstituted aryl group, or a substitutedor unsubstituted heterocyclic group. It is preferable that R^(d) is ahydrogen atom and Q^(d) is a single bond, in other words, Y representedby —C(-Q^(d)-R^(d))— is preferably unsubstituted methine.

Examples of the compound represented by Formula (1) and (2) includecompounds in which Y is a nitrogen atom, and -Q^(a)-R^(a) and-Q^(c)-R^(c) each are groups other than —OH and —SH.

Examples of the compound represented by Formula (1) or (2) are notlimited to those having structures specified by Formula (1) or (2) andinclude those having resonance structures of the heterocyclic skeletonsspecified by Formula (1) or (2). Furthermore, examples of the compoundrepresented by Formula (1) or (2) include those having structures ofwhich the heterocyclic skeletons resonating with -Q^(a)-R^(a) or-Q^(c)-R^(c). The same applies to compounds represented by Formulae (3)to (12) described below.

In Formulae (1) and (2), R¹, R², R³, and R⁴ each independently representa hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, anaryl group, or a heterocyclic group, wherein any two of R¹, R², R³, andR⁴ are optionally bonded to each other to form a ring.

When R¹, R², R³, or R⁴ each represents the alkyl group, the alkyl grouppreferably has 1 to 20 carbon atoms, more preferably 1 to 8 carbonatoms, and most preferably 1 to 4 carbon atoms. when R¹, R², R³, or R⁴each represents the alkyl group, one carbon atom or non-adjacent two ormore carbon atoms are each optionally replaced by a hetero atom selectedfrom oxygen atom, sulfur atom, and nitrogen atom (including —NH— and—N(R)— (R: alkyl group)). For example, R¹, R², R³, and R⁴ may each be analkylene (e.g., ethylene or propylene) oxy group.

When R¹, R², R³, or R⁴ each represents the alkenyl group, the alkenylgroup preferably has 2 to 20 carbon atoms, more preferably 2 to 8 carbonatoms, and most preferably 2 to 4 carbon atoms.

When R¹, R², R³, or R⁴ each represents the alkynyl group, the alkynylgroup preferably has 2 to 20 carbon atoms, more preferably 2 to 8 carbonatoms, and most preferably 2 to 4 carbon atoms.

When R¹, R², R³, or R⁴ each represents the aryl group, the aryl grouppreferably has 6 to 24 carbon atoms, more preferably 6 to 18 carbonatoms, and most preferably 6 to 10 carbon atoms, from the viewpoint ofreducing humidity dependency. Specifically, the aryl group is preferablya benzene ring or a naphthalene ring and most preferably a benzene ring.

When R¹, R², R³, or R⁴ each represents the heterocyclic group, theheterocyclic group preferably has 4 to 20 carbon atoms, more preferably4 to 10 carbon atoms, and most preferably 4 to 6 carbon atoms, from theviewpoint of reducing humidity dependency. Specific examples of theheterocyclic group include pyrrolyl group, pyrrolidino group, pyrazolylgroup, pyrazolidino group, imidazolyl group, piperazino group, andmorpholino group.

In Formulae (1) and (2), it is preferable that R¹, R², R³ and R⁴ be eachindependently a hydrogen atom, an alkyl group, an aryl group, or aheterocyclic group.

R¹, R², R³, and R⁴ each optionally further have one or moresubstituents, if possible. Examples of the substituent optionallypossessed by R¹, R², R³, or R⁴ include those belonging to thesubstituent group T mentioned above.

In Formulae (1) and (2), it is preferable that R¹, R², R³, and R⁴ beeach independently a hydrogen atom, a substituted or unsubstituted alkylgroup, a substituted or unsubstituted aryl group, or a substituted orunsubstituted heterocyclic group.

Either R¹ or R² and either R³ or R⁴ are each preferably a hydrogen atomor a substituted or unsubstituted alkyl group, and most preferably ahydrogen atom. The other substituents are preferably substituted orunsubstituted aryl groups from the viewpoint of reducing humiditydependency.

In Formulae (1) and (2), X² and X⁴ each independently represent a singlebond or a divalent linking group; X¹ and X³ each represent a single bondor a group selected from the divalent linking group G¹ shown below.

Examples of the each divalent linking groups represented by X² or X⁴include alkylene groups (preferably having 1 to 30 carbon atoms, morepreferably 1 to 3 carbon atoms, and most preferably two carbon atoms)and arylene groups (preferably having 6 to 30 carbon atoms and morepreferably 6 to 10 carbon atoms). Examples of the divalent linkinggroups represented by X¹ or X³ include those belonging to the divalentlinking group G¹.

In each formula, the side indicated by symbol * is a bonding site to thenitrogen atom introduced into the pyrimidine ring or pyridine ring inthe compound represented by each formula; and R^(g) represents ahydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, anaryl group, or a heterocyclic group. The preferred range of the numberof carbon atoms in each group is the same as the preferred range of thenumber of carbon atoms in each group represented by X^(a) or X^(b).

Preferably, X¹ and X³ are each independently selected from a divalentlinking group G².

Symbols in the divalent linking group G² are synonymous with those inthe divalent linking group G¹.

Preferably, X¹ and X³ are each independently a single bond or a groupselected from the divalent linking group G¹. More preferably, X² is asingle bond, X¹ represents a group selected from the divalent linkinggroup G¹, X⁴ is a single bond, and X³ represents a group selected fromthe divalent linking group G¹.

More preferably, in such a case, X¹ and X³ are each independently anyone of —CO—, —COO—, and —CO(NR^(g))— and most preferably —CO—.

For example, when X¹ is a prescribed divalent linking group (mostpreferably —CO—) and when X² is a single bond, R¹ is preferably asubstituted or unsubstituted alkyl group, a substituted or unsubstitutedaryl group, or a substituted or unsubstituted heterocyclic group(preferably a substituted or unsubstituted aryl group, from theviewpoint of reducing humidity dependency), and R² is preferably ahydrogen atom. Similarly, when X³ is a prescribed divalent linking group(preferably —CO—) and when X⁴ is a single bond, R³ is preferably asubstituted or unsubstituted alkyl group, a substituted or unsubstitutedaryl group, or a substituted or unsubstituted heterocyclic group(preferably a substituted or unsubstituted aryl group, from theviewpoint of reducing humidity dependency) and R⁴ is preferably ahydrogen atom.

Furthermore, in Formula (1), when X¹ is a prescribed divalent linkinggroup, R¹ is preferably an aryl group, in particular, a substituted orunsubstituted phenyl group. The aryl group optionally has one or moresubstituents selected from the substituent group T. The substituent maybe introduced into any position and may be introduced into one of theortho-, meta-, and para-positions relative to X¹. Preferred examples ofthe substituent include halogen atoms, a hydroxyl group, a carbamoylgroup, a sulfamoyl group, alkyl groups (preferably alkyl group having 1to 8 carbon atoms), alkoxy groups (preferably alkoxy group having 1 to 8carbon atom), alkylamino groups (preferably alkylamino groups having 1to 8 carbon atoms), and dialkylamino groups (preferably dialkylaminogroups having 1 to 8 carbon atoms). Alkyl groups (preferably alkylgroups having 1 to 8 carbon atoms) and alkoxy groups (preferably alkoxygroups having 1 to 8 carbon atoms) are more preferred, and alkyl groupsand alkoxy groups having 1 to 4 carbon atoms are most preferred.

In Formula (2), when X¹ and X³ are divalent linking groups, R¹ and R³are preferably aryl groups, in particular, substituted or unsubstitutedphenyl groups. The aryl group optionally has one or more substituentsselected from the substituent group T. The substituent may be introducedinto any position and may be introduced into one of the ortho-, meta-,and para-positions relative to X¹ or X³. Preferred examples of thesubstituent include halogen atoms, a hydroxyl group, a carbamoyl group,a sulfamoyl group, alkyl groups (preferably alkyl groups having 1 to 8carbon atoms), alkoxy groups (preferably alkoxy groups having 1 to 8carbon atoms), alkylamino groups (preferably alkylamino groups having 1to 8 carbon atoms), and dialkylamino groups (preferably dialkylaminogroups having 1 to 8 carbon atoms). Alkyl groups (preferably alkylgroups having 1 to 8 carbon atoms) and alkoxy groups (preferably alkoxygroups having 1 to 8 carbon atoms) are more preferred, and alkyl groupsand alkoxy groups having 1 to 4 carbon atoms are most preferred.

In Formulae (1) and (2), when all of X¹, X², X³, and X⁴ are not any ofthe divalent linking groups belonging to the divalent linking group G¹,X¹, X², X³, and X⁴ are preferably single bonds, and R¹, R², R³, and R⁴respectively bonding to X¹, X², X³, and X⁴ are preferably hydrogenatoms. In Formula (2), however, when X¹ and X² are single bonds and whenR¹ and R² are hydrogen atoms, X³ and X⁴ are single bonds, and R³ and R⁴are hydrogen atoms. In Formula (1), when X¹ and X² are single bonds andwhen R¹ and R² are hydrogen atoms, -Q^(c)-R^(c) is —NH₂.

Examples of the compound represented by Formula (1) include compoundsrepresented by Formula (3).

Symbols in Formula (3) are each synonymous with those in Formula (1),and the preferred ranges and specific examples are also the same.Examples of the compound represented by Formula (3) include compounds ofwhich -Q^(a)-R^(a) is a group other than —OH and —SH, provided thatcompounds where only one of -Q^(c)-R^(c) and —N(X¹R¹)X²R² is —NH₂ andcompounds where both -Q^(c)-R^(c) and —N(X¹R¹)X²R² are not —NH₂ and-Q^(a)-R^(a) is —NH₂ are excluded.

Examples of the compound represented by Formula (1) include compoundsrepresented by Formula (4).

Symbols in Formula (4) are each synonymous with those in Formula (1),and the preferred ranges and specific examples are also the same,provided that compounds where only one of -Q^(c)-R^(c) and —N(X¹R¹)X²R²is —NH₂ are excluded.

Examples of the compound represented by Formula (1) include compoundsrepresented by Formula (3a).

Symbols in Formula (3a) are each synonymous with those in Formula (1),and the preferred ranges and specific examples are also the same.

Examples of the compound represented by Formula (1) include compoundsrepresented by Formula (3b).

Symbols in Formula (3b) are each synonymous with those in Formula (1),and the preferred ranges and specific examples are also the same.

Examples of the compound represented by Formula (1) include compoundsrepresented by Formula (3c).

Symbols in Formula (3c) are each synonymous with those in Formula (1),and the preferred ranges and specific examples are also the same.

In Formula (1), Q^(a) is preferably a single bond or a divalent linkinggroup represented by —O—, —S—, —N(X^(a)—R^(h))—, or—N(X^(a)—R^(h))—X^(b)—; more preferably a single bond or —O—, —S—, —NH—,or —N(R)— (wherein R is an alkyl group having 1 to 8 carbon atoms andpreferably 1 to 4 carbon atoms); and most preferably a single bond or—O—. R^(a) is preferably a hydrogen atom, a halogen atom, an alkyl grouphaving 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms,an alkynyl group having 2 to 8 carbon atoms, an aryl group having 6 to18 carbon atoms (e.g., a benzene ring or naphthalene ring group), or aheterocyclic group having 4 to 10 carbon atoms (e.g., a pyrrolyl group,a pyrrolidino group, a pyrazolyl group, a pyrazolidino group, animidazolyl group, a piperazino group, or a morpholino group); morepreferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms;and most preferably an alkyl group having 1 to 4 carbon atoms. The alkylgroup may be substituted, but is preferably unsubstituted. Examples ofthe substituent include a hydroxyl group, a cyano group, alkoxy groups,alkoxycarbonyl groups, and an amino group. When Q^(a) is —N(R)—, R^(a)is optionally bonded to R to form a ring (e.g., 5- or 6-membered ring).Examples of the compound represented by Formula (1) include compounds ofwhich -Q^(a)-R^(a) is a group other than —OH and —SH.

Preferred examples of -Q^(a)-R^(a) include —Cl, —CH₃, -(t)C₄H₉, —OH,—OCH₃, —OC₂H₅, —NH₂, —NHCH₃, NHC₂H₅, —NHC₃H₇, —NHC₄H₉, —N(CH₃)₂, and—N(C₂H₅)₂. More preferred examples are —Cl, —CH₃, —OH, —OCH₃, NH₂,—NHCH₃, and NHC₂H₅; and most preferred examples are —CH₃ and —OCH₃.

Examples of the compound represented by Formula (1) include compoundsrepresented by Formula (5-1).

Symbols in Formula (5-1) are each synonymous with those in Formula (1),and the preferred ranges and specific examples are also the same,provided that compounds where only one of -Q^(c)-R^(c) and -Q^(a)-R^(a)is NH₂ are excluded.

Ar¹ represents an aryl group. The aryl group is preferably a substitutedor unsubstituted phenyl or naphthyl group and more preferably asubstituted or unsubstituted phenyl group. The aryl group represented byAr¹ optionally has one or more substituents. Examples of the substituentinclude those belonging to the substituent group T, and preferredexamples of the substituent are each the same as those possessed by R¹or R³ in Formula (2).

Examples of the compound represented by Formula (1) include compoundsrepresented by Formula (5-2).

Symbols in Formula (5-2) are each synonymous with those in Formula (1),and the preferred ranges and specific examples are also the same. Ar²represents an aryl group.

Preferred examples of the compound represented by Formula (1) or (2)include compounds represented by Formula (6).

Symbols in Formula (6) are each synonymous with those in Formula (2).Ar¹ and Ar² each represent an aryl group. Preferred examples of Q^(a)and R^(a) are the same as those of each group in Formula (3c).

The aryl group represented by Ar¹ or Ar² is preferably a substituted orunsubstituted phenyl or naphthyl group and more preferably a substitutedor unsubstituted phenyl group. The aryl group represented by Ar¹ or Ar²optionally has one or more substituents. Examples of the substituentinclude those belonging to the substituent group T, and preferredexamples of the substituent are the same as those possessed by R¹ or R³in Formula (2). Ar¹ and Ar² may be the same or different from eachother. For example, one of them may be an unsubstituted aryl group, andthe other may be the same aryl group having one or more substituents.Alternatively, both of them may be the same aryl groups having differentsubstituents.

In an example of synthesizing a compound having Ar¹ and Ar² differentfrom each other in Formula (6) using the respective reagents forintroducing Ar¹ and Ar², a mixture of three or four compounds, i.e., acompound having two Ar¹s, a compound having two Ar²s, and one or twocompounds having Ar¹ and Ar² (when Y is a nitrogen atom, two compoundsare specified), may be prepared. In the present invention, such amixture may be directly used as an additive for polymer films. That is,a mixture of compounds represented by Formulae (6a) to (6d) (or Formulae(6a) to (6c) when Y is a methine group) may be used as an additive.

Symbols in Formulae (6a) to (6d) are each synonymous with those inFormula (2), provided that Ar¹ and Ar² represent different groups fromeach other.

Q^(a) is preferably a single bond or a divalent linking grouprepresented by —O—, —S—, —N(X^(a)—R^(h))—, or —N(X^(a)—R^(h))—X^(b)—;more preferably a single bond or —O—, —S—, —NH—, or —N(R)— (wherein R isan alkyl group having 1 to 8 carbon atoms and preferably 1 to 4 carbonatoms); and most preferably a single bond or —O—. R^(a) is preferably ahydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbonatoms, an alkenyl group having 2 to 8 carbon atoms, an alkynyl grouphaving 2 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms(e.g., a benzene ring or naphthalene ring group), a heterocyclic grouphaving 4 to 10 carbon atoms (e.g., a pyrrolyl group, a pyrrolidinogroup, a pyrazolyl group, a pyrazolidino group, an imidazolyl group, apiperazino group, or a morpholino group); and more preferably a hydrogenatom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms (morepreferably an alkyl group having 1 to 4 carbon atoms). The alkyl groupmay be substituted, but is preferably unsubstituted. Examples of thesubstituent include a hydroxyl group, a cyano group, alkoxy groups,alkoxycarbonyl groups, and an amino group. When Q^(a) is —N(R)—, R^(a)is optionally bonded to R to form a ring (e.g., 5- or 6-membered ring).Examples of the compound represented by Formula (6) include compounds ofwhich -Q^(a)-R^(a) is a group other than —OH and —SH.

Preferred examples of -Q^(a)-R^(a) include —Cl, —CH₃, -(t)C₄H₉, —OH,—OCH₃, —OC₂H₅, —NH₂, —NHCH₃, NHC₂H₅, —NHC₃H₇, —NHC₄H₉, —N(CH₃)₂, and—N(C₂H₅)₂. More preferred examples are —Cl, —CH₃, —OH, —OCH₃, NH₂,—NHCH₃, and NHC₂H₅; and most preferred examples are —CH₃ and —OCH₃.

Preferred examples of the compound represented by Formula (6) includecompounds represented by Formula (6-1).

Symbols in Formula (6-1) are each synonymous with those in Formula (6);and Ar¹ and Ar² represent aryl groups.

Q^(aa) represents a single bond or —O—, —NH—, or —N(R)— (wherein R is analkyl group having 1 to 8 carbon atoms).

R^(aa) represents a hydrogen atom, a halogen atom, or an alkyl grouphaving 1 to 8 carbon atoms.

The preferred ranges of Ar¹ and Ar² are the same as those shown inFormula (6).

The preferred ranges of Q^(aa) and R^(aa) are respectively the same asthose of Q^(a) and R^(a) in Formula (6).

The compounds represented by Formula (6) and Formulae (7-1), (7-2), and(8) to (10) described below have high retardation-enhancing effects.Polymer films containing these compounds and thereby having controlledRe and/or Rth are characterized by further reduced fluctuations in Reand/or Rth depending on humidity.

Preferred examples of the compound represented by Formula (2) includecompounds represented by Formula (7-1).

Symbols, Y, Q^(aa), and R^(aa), in Formula (7-1) are each synonymouswith those in Formula (6-1); and R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ eachindependently represent a hydrogen atom, a halogen atom, a carbamoylgroup, a sulfamoyl group, an alkyl group having 1 to 8 carbon atoms, oran alkoxy group having 1 to 8 carbon atoms.

R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each preferably a hydrogen atom, analkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8carbon atoms; and most preferably a hydrogen atom, an alkyl group having1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. R¹¹to R¹⁶ may be the same as or different from each other. For example, allof R¹¹ to R¹³ are hydrogen atoms, and at least one of R¹⁴ to R¹⁶ is asubstituent mentioned above; all of R¹⁴ to R¹⁶ are hydrogen atoms, andat least one of R¹¹ to R¹³ is a substituent mentioned above; or at leastone of R¹¹ to R¹³ and at least one of R¹⁴ to R¹⁶ are substituentsmentioned above and different from each other.

The sites into which R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ are introduced maybe any of the ortho-, meta-, and para-positions relative to —C(═O)—, butfrom the viewpoint of the effect of improving the humidity dependency,the site of the substitution is preferably a position other than theortho-position.

Preferred examples of -Q^(aa)-R^(aa) in Formula (7-1) include —Cl, —CH₃,-(t)C₄H₉, —OH, —OCH₃, —OC₂H₅, —NH₂, —NHCH₃, NHC₂H₅, —NHC₃H₇, —NHC₄H₉,—N(CH₃)₂, and —N(C₂H₅)₂. More preferred examples are —Cl, —CH₃, —OH,—OCH₃, NH₂, —NHCH₃, and NHC₂H₅; and most preferred examples are —CH₃ and—OCH₃.

Furthermore, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ in Formula (7-1) are eachpreferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms,or an alkoxy group having 1 to 8 carbon atoms and most preferably ahydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxygroup having 1 to 4 carbon atoms.

Preferred examples of the compound represented by Formula (2) includecompounds represented by Formula (7-2).

Symbols in Formula (7-2) are each synonymous with those in Formula (2);Q^(a) represents a single bond or a divalent linking group; R^(a7)represents an alkyl group having 1 to 8 carbon atoms; and R¹¹, R¹², R¹³,R¹⁴, R¹⁵ and R¹⁶ each represent a hydrogen atom, a halogen atom, acarbamoyl group, a sulfamoyl group, an alkyl group having 1 to 8 carbonatoms, or an alkoxy group having 1 to 8 carbon atoms.

R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each preferably a hydrogen atom, analkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8carbon atoms and more preferably a hydrogen atom, an alkyl group having1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. R¹¹to R¹⁶ may be the same as or different from each other. For example, allof R¹¹ to R¹³ are hydrogen atoms, and at least one of R¹⁴ to R¹⁶ is asubstituent mentioned above; all of R¹⁴ to R¹⁶ are hydrogen atoms, andat least one of R¹¹ to R¹³ is a substituent mentioned above; or at leastone of R¹¹ to R¹³ and at least one of R¹⁴ to R¹⁶ are substituentsmentioned above and different from each other.

Q^(a) is preferably a single bond or a divalent linking grouprepresented by —O—, —S—, —N(X^(a)—R^(h))—, or —N(X^(a)—R^(h))—X^(b)—,more preferably a single bond or —O—, —S—, —NH—, or —N(R)— (wherein R isan alkyl group having 1 to 8 carbon atoms and preferably 1 to 4 carbonatoms), and most preferably a single bond or —O— or —NH—.

Preferred examples of the compound represented by Formula (7-1) or (7-2)include compounds represented by Formulae (8) to (10).

Symbols in Formulae (8) to (10) are each synonymous with those inFormulae (7-1) and (7-2), and R^(a8), R^(a9), and R^(a10) each representan alkyl group having 1 to 8 carbon atoms (preferably 1 to 4 carbonatoms).

Examples of the compound represented by Formula (1) include compoundshaving —NH₂ as each of -Q^(c)-R^(c) and —N(X¹R¹)X²R², i.e., compoundsrepresented by Formula (11). Though the effect of the compoundsrepresented by Formula (11) (preferably represented by Formula (11a)) onenhancing the Re and the Rth is lower than those of compoundsrepresented by Formulae (6) to (10), such compounds are preferably usedin application that needs relatively low Re and Rth.

Symbols in Formulae are each synonymous with those in Formula (2), andthe preferred ranges and preferred examples are also the same. Examplesof the compound represented by Formula (11) or (11a) include compoundsof which -Q^(a)-R^(a) is a group other than —OH and —SH.

The compounds represented by Formula (12) also have highretardation-enhancing effects as in the compounds represented byFormulae (6), (7-1), (7-2), and (8) to (10).

The groups in the formula are each synonymous with those in Formulae (1)to (6), (7-1), (7-2), and (8) to (10), and the preferred ranges are alsothe same. Q¹² is a single bond or —NH—, —O—, or —S—; and R¹² is ahydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl grouphaving 6 to 18 carbon atoms (e.g., a benzene ring or naphthalene ringgroup), or a heterocyclic group having 4 to 10 carbon atoms (e.g., apyrrolyl group, a pyrrolidino group, a pyrazolyl group, a pyrazolidinogroup, an imidazolyl group, a piperazino group, or a morpholino group),preferably an alkyl group having 1 to 8 carbon atoms or an aryl grouphaving 6 to 18 carbon atoms. When Q¹² is a single bond or —O— or —S—,R¹² is preferably a hydrogen atom or an alkyl group having 1 to 8 carbonatoms; and when Q¹² is —NH—, R¹² is preferably an alkyl group having 1to 8 carbon atoms and more preferably an aryl group having 6 to 18carbon atoms (more preferably a benzene ring group). Examples of thecompound represented by Formula (12) include compounds of which-Q^(a)-R^(a) is a group other than —OH and —SH, provided that compoundswhere only one of -Q¹²-R¹² and -Q^(a)-R^(a)— is —NH₂ are excluded.

The compound of the present invention is characterized by a pyrimidinering or a pyridine ring having a prescribed substituent at a prescribedposition thereon. Among the compounds of the present invention,compounds represented by partial structure Formula (A) have particularlyhigh effects of reducing the dependency of Re and Rth on humidity. Suchcompounds are more preferably represented by partial structure Formula(B) and most preferably by partial structure Formula (C). Y in Formulae(A) to (C) is synonymous with Y in Formula (1), in other words, Y is —N—or —C(-Q^(d)-R^(d))— (definitions of Q^(d) and R^(d) are as describedabove).

These partial structures are characterized in that a hydrogen-bond donorsite and a hydrogen-bond acceptor site are located sterically close toeach other. Such a structure allows formation of hydrogen bonds withwater or hydroxyl groups at multiple points. In particular, compoundshaving partial structure (B) or (C) can have a conformation capable offorming a circular hydrogen-bond pair with water or a hydroxyl group.These structural characteristics are likely to cause capture of watermolecules in a polymer film or cause strong interaction with hydroxylgroups in a polymer or water bonded to a polymer through a hydrogen bondand thereby to express the effect of reducing the fluctuation in Re andRth caused by a change in humidity of the operating environment.

The steric structure of the compound represented by Formula (1) used inthe present invention is also important.

In order to express the effect of enhancing the retardation (Re and/orRth) of a polymer film, a compound having high flatness and a rodstructure is preferred. In order to express the effect of reducing thefluctuation in Re and Rth caused by a change in humidity of theoperating environment of a polymer film, similarly, a compound havinghigh flatness and a compact structure is preferred. If the compound issterically bulky, the inventive compound is prevented by the polymerchain from approaching to effectively capture water molecules.

Specific examples of the usable compound represented by Formula (1) ofthe present invention are shown, but not limited to, below.

(1b-1) The Compound Group B

The compound group B is represented by Formula (I) and is preferablyrepresented by Formula (II).

In Formula (I), Y represents —N— or —C(-Q^(d)-R^(d))—; Q^(a), Q^(b),Q^(c), and Q^(d) each independently represent a single bond or adivalent linking group; R^(a), R^(b), R^(c), and R^(d) eachindependently represent a hydrogen atom, an alkyl group, an alkenylgroup, an alkynyl group, an aryl group, a cyano group, a halogen group,or a heterocyclic group, wherein R^(a) and R^(b) are optionally bondedto each other to form a ring, or R^(a) and R^(d) are optionally bondedto each other to form a ring; X² represents a single bond or a divalentlinking group; X¹ represents a single bond or a divalent group selectedfrom the divalent linking group G¹ shown below; and R¹ and R² eachindependently represent a hydrogen atom, an alkyl group, an alkenylgroup, an alkynyl group, an aryl group, or a heterocyclic group, whereinR¹ and R² are optionally bonded to each other to forma ring, providedthat one of -Q^(c)-R^(c) and N(X¹R¹)X²R² is —NH₂ and both are notsimultaneously —NH₂ and that when Y is a nitrogen atom and whenN(X¹R¹)X²R² is —NH₂, -Q^(a)-R^(a) is not —NH₂. That is, compounds nothaving amine and diamine compounds having partial structures shown beloware excluded from the compounds represented by Formula (I).

In the formulae, each symbol * denotes a position to which any one of-Q^(a)-R^(a), -Q^(b)-R^(b), -Q^(c)-R^(c), and -Q^(d)-R^(d) bonds.

Symbols in Formula (II) are each synonymous with those in Formula (I); Yrepresents —N— or —C(-Q^(d)-R^(d))—, and Z represents —N— or—C(-Q^(b)-R^(b))—, provided that Y and Z are not simultaneously —N—; X¹represents a single bond or a linking group selected from the groupconsisting of divalent linking groups represented by the divalentlinking group G²; X² represents a single bond or a divalent linkinggroup; R¹ and R² each independently represent a hydrogen atom, an alkylgroup, an alkenyl group, an alkynyl group, an aryl group, or aheterocycle; at least one of —X¹—R¹ and —X²—R² is a substituent otherthan a hydrogen atom; Q^(a), Q^(b), and Q^(d) each independentlyrepresent a single bond or —O—, —S—, or —NR′—, wherein R′ represents ahydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, anaryl group, or a heterocycle, wherein Q^(a) and R^(a), Q^(d) and R^(d),or Q^(b) and R^(b) are optionally bonded to each other to form a ring,or -Q^(a)-R^(a)—R^(d)-Q^(d)- or -Q^(a)-R^(a)—R^(b)-Q^(b)- optionallyforms a ring; and R^(a) represents a hydrogen atom, a halogen, an alkylgroup, an alkenyl group, an alkynyl group, an aryl group, or aheterocycle, provided that when Z is —N—, -Q^(a)-R^(a) represents asubstituent other than an amino group; R^(b) and R^(d) eachindependently represent a hydrogen atom, an alkyl group, an alkenylgroup, an alkynyl group, an aryl group, or a heterocycle.

In Formula (I), when Y is a methine group, in other words, when Y is—C(-Q^(d)-R^(d))—, the 6-membered ring in the formula is a pyridinering; and when Y is —N—, the 6-membered ring in the formula is apyrimidine ring. In Formula (I), when Y is —N— and when —N(X¹R¹)X²R² is—NH₂, -Q^(a)-R^(a) is not —NH₂.

In Formula (II), Y and Z are not simultaneously —N—, when Y and Z aremethine groups optionally having substituents, in other words, when Yand Z are —C(-Q^(d)-R^(d))— or —C(-Q^(b)-R^(b))—, the 6-membered ring inthe formula is a pyridine ring; and when Y or Z is —N—, the 6-memberedring in the formula is a pyrimidine ring. In Formula (II), when Z is—N—, -Q^(a)-R^(a) is not —NH₂.

Examples of the compound represented by Formula (I) or (II) includecompounds not having the partial structures represented by Formula (a)or (b). In Formulae (a) and (b), each symbol * indicates a position intowhich an atom or a residue can be introduced.

Examples of the structures of the compounds represented by Formula (I)and (II) are not limited to those specified by Formula (I) and (II) andinclude resonance structures of the heterocyclic skeletons specified byFormula (I) or (II). The examples of the structures of the compoundsrepresented by Formula (I) and (II) also include structures in which theheterocyclic skeletons specified by Formula (I) and (II) resonate withsubstituents bonded to atoms constituting the rings. The same applies tothe compounds represented by formulae described below.

In Formulae (I) and (II), examples of the divalent linking grouprepresented by Q^(a), Q^(b), Q^(c), or Q^(d) include divalent linkinggroups represented by —O—, —S—, —N(X^(a)—R^(h))—, or—N(X^(a)—R^(h))—X^(b)—, wherein X^(a) and X^(b) each represent a singlebond or a divalent linking group. Examples of the divalent linking grouprepresented by X^(a) or X^(b) include —CO—, —COO—, and —CONH—. R^(h)represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms,an alkenyl group having 2 to 8 carbon atoms, an alkynyl group having 2to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or aheterocyclic group having 2 to 10 carbon atoms. Preferred examples ofthe divalent linking group represented by Q^(a), Q^(b), Q^(c), or Q^(d)include a single bond, —O—, —N(X^(a)—R^(h))—, and—N(X^(a)—R^(h))—X^(b)—; and a single bond, —O—, —NH—, and —NH—X^(b)— areparticularly preferred. Preferred examples of —NH—X^(b)— include—NH—CO—, —NH—COO—, —NH—CONH—, and —NH—SO₂—; and —NH—CO— and —NH—COO— areparticularly preferred.

In Formulae (I) and (II), R^(a), R^(b), R^(c), and R^(d) each representa hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, anaryl group, a cyano group, a halogen group, or a heterocyclic group,wherein R^(a) and R^(b) are optionally bonded to each other to form aring, or R^(a) and R^(d) are optionally bonded to each other to form aring.

When R^(a), R^(b), R^(c), or R^(d) represents the alkyl group, the alkylgroup preferably has 1 to 20 carbon atoms, more preferably 1 to 8 carbonatoms, and most preferably 1 to 4 carbon atoms. When R^(a), R^(b),R^(c), or R^(d) represents the alkyl group, one carbon atom ornon-adjacent two or more carbon atoms are each optionally replaced by ahetero atom selected from oxygen atom, sulfur atom, and nitrogen atom(including —NH— and —N(R)— (R: alkyl group)). For example, R^(a) andR^(b) may each be an alkylene (e.g., ethylene or propylene) oxy group.

When R^(a), R^(b), R^(c), or R^(d) represents the alkenyl group, thealkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to8 carbon atoms, and most preferably 2 to 4 carbon atoms.

When R^(a), R^(b), R^(c), or R^(d) represents the alkynyl group, thealkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to8 carbon atoms, and most preferably 2 to 4 carbon atoms.

When R^(a), R^(b), R^(c), or R^(d) represents the aryl group, the arylgroup preferably has 6 to 24 carbon atoms, more preferably 6 to 18carbon atoms, and most preferably 6 to 10 carbon atoms, from theviewpoint of reducing humidity dependency. Specifically, the aryl groupis preferably a benzene ring or a naphthalene ring and most preferably abenzene ring.

When R^(a), R^(b), R^(c), and R^(d) are each a halogen group, any offluorine atom, chlorine atom, bromine atom, and iodine atom can be used,and chlorine atom are particularly preferred.

When R^(a), R^(b), R^(c), or R^(d) represents the heterocyclic group,the heterocyclic group preferably has 4 to 20 carbon atoms, morepreferably 4 to 10 carbon atoms, and most preferably 4 to 6 carbonatoms, from the viewpoint of reducing humidity dependency. Specificexamples of the heterocyclic group include pyrrolyl group, pyrrolidinogroup, pyrazolyl group, pyrazolidino group, imidazolyl group, piperazinogroup, and morpholino group.

R^(a) and R^(b) are optionally bonded to each other to form a ring,R^(a) and R^(d) are optionally bonded to each other to form a ring. Thering to be formed may be a hydrocarbon ring or a heterocycle and ispreferably a 5-membered or 6-membered ring.

R^(a), R^(b), R^(c), and R^(d) each optionally further have one or moresubstituents, if possible. Examples of the substituent optionallypossessed by R^(a), R^(b), R^(c), or R^(d) include those shown in thesubstituent group T mentioned above.

In Formula (I), R^(a), R^(b), R^(c), and R^(d) are each preferably ahydrogen atom, a halogen atom, or a substituted or unsubstituted alkylgroup. In Formula (II), R^(c) is preferably a hydrogen atom. In oneembodiment of compounds belonging to the compound group B, R^(d) shouldpreferably be a hydrogen atom and Q^(d) be a single bond, in otherwords, —C(-Q^(d)-R^(d))— represented by Y is unsubstituted methine. Inone embodiment of the present invention, R^(b) should preferably be ahydrogen atom and Q^(b) be a single bond, in other words,—C(-Q^(b)-R^(b))— represented by Y is unsubstituted methine.

Examples of the compound represented by Formula (I) or (II) includescompounds in which Y is a nitrogen atom and -Q^(a)-R^(a) and-Q^(c)-R^(c) are each a group other than —OH and —SH.

In Formulae (I) and (II), -Q^(a)-R^(a) is preferably -Q^(aa)-R^(aa).Q^(aa) represents a single bond or —O—, —NH—, or —N(R)— (wherein R is analkyl group having 1 to 8 carbon atoms). R^(aa) represents a hydrogenatom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms.

In Formulae (I) and (II), R¹ and R² each represent a hydrogen atom, analkyl group, an alkenyl group, an alkynyl group, an aryl group, or aheterocyclic group, wherein R¹ and R² are optionally bonded to eachother to form a ring.

When R¹ or R² each represents the alkyl group, the alkyl grouppreferably has 1 to 20 carbon atoms, more preferably 1 to 8 carbonatoms, and most preferably 1 to 4 carbon atoms. When R¹ or R² eachrepresents the alkyl group, one carbon atom or non-adjacent two or morecarbon atoms are each optionally replaced by a hetero atom selected fromoxygen atom, sulfur atom, and nitrogen atom (including —NH— and —N(R)—(R: alkyl group)). For example, R¹ and R² may each be an alkylene (e.g.,ethylene or propylene) oxy group.

When R¹ or R² each represents the alkenyl group, the alkenyl grouppreferably has 2 to 20 carbon atoms, more preferably 2 to 8 carbonatoms, and most preferably 2 to 4 carbon atoms.

When R¹ or R² each represents the alkynyl group, the alkynyl grouppreferably has 2 to 20 carbon atoms, more preferably 2 to 8 carbonatoms, and most preferably 2 to 4 carbon atoms.

When R¹ or R² each represents the aryl group, the aryl group preferablyhas 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, and mostpreferably 6 to 10 carbon atoms, from the viewpoint of reducing humiditydependency. Specifically, the aryl group is preferably a benzene ring ora naphthalene ring and most preferably a benzene ring.

When R¹ or R² each represents the heterocyclic group, the heterocyclicgroup preferably has 4 to 20 carbon atoms, more preferably 4 to 10carbon atoms, and most preferably 4 to 6 carbon atoms, from theviewpoint of reducing humidity dependency. Specific examples of theheterocyclic group include pyrrolyl group, pyrrolidino group, pyrazolylgroup, pyrazolidino group, imidazolyl group, piperazino group, andmorpholino group.

In Formulae (I) and (II), R¹ and R² are each preferably a hydrogen atom,an alkyl group, an aryl group, or a heterocyclic group, provided thatwhen -Q^(c)-R^(c) is —NH₂ and when —X¹ and —X² represent single bonds,at least one of R¹ and R² is not a hydrogen atom.

R¹ and R² each optionally further have one or more substituents, ifpossible. Examples of the substituent optionally possessed by R¹ or R²include those shown in the substituent group T mentioned above.

In Formulae (I) and (II), R¹ and R² are each preferably a hydrogen atom,a substituted or unsubstituted alkyl group, a substituted orunsubstituted aryl group, or a substituted or unsubstituted heterocyclicgroup.

One of R¹ and R² is preferably a hydrogen atom or a substituted orunsubstituted alkyl group and more preferably a hydrogen atom. From theviewpoint of reducing humidity dependency, the other is preferably asubstituted or unsubstituted aryl group.

In Formulae (I) and (II), X² represents a single bond or a divalentlinking group; and X¹ represents a single bond or a group selected fromthe divalent linking group G¹ shown below.

Examples of the divalent linking group represented by X² includealkylene groups (preferably having 1 to 30 carbon atoms, more preferably1 to 3 carbon atoms, and most preferably 2 carbon atoms) and arylenegroups (preferably having 6 to 30 carbon atoms and more preferably 6 to10 carbon atoms); and examples of the divalent linking group representedby X¹ include those belonging to the divalent linking group G¹ andpreferably those belonging to the divalent linking group G².

In each formula, the side indicated by symbol * is a bonding site to thenitrogen atom of the substituent introduced into the pyrimidine ring orpyridine ring in the compound represented by each formula; and R^(g)represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynylgroup, an aryl group, or a heterocyclic group. The preferred range ofthe number of carbon atoms in each group is the same as the preferredrange of the carbon atoms in the groups represented by X^(a) and X^(b).

X¹ is preferably a single bond or a group selected from the divalentlinking group G¹. More preferably, X² is a single bond and X¹ representsa group selected from the divalent linking group G¹.

More preferably, in such a case, X¹ is any one of —CO—, —COO—, and—CO(NR^(g))— and most preferably —CO—.

For example, when X¹ is a prescribed divalent linking group (preferably—CO—) and when X² is a single bond, R¹ is a substituted or unsubstitutedalkyl group, a substituted or unsubstituted aryl group, or a substitutedor unsubstituted heterocyclic group (from the viewpoint of reducinghumidity dependency, preferably a substituted or unsubstituted arylgroup) and R² is preferably a hydrogen atom.

Furthermore, in Formula (I), when X¹ is a prescribed divalent linkinggroup, R¹ is preferably an aryl group, in particular, a phenyl group.The aryl group optionally has one or more substituents selected from thesubstituent group T. The substituent may be introduced into any positionand may be introduced into one of the ortho-, meta-, and para-positionsrelative to X¹. Preferred examples of the substituent include halogenatoms, a hydroxy group, a carbamoyl group, a sulfamoyl group, alkylgroups (preferably alkyl groups having 1 to 8 carbon atoms), alkoxygroups (preferably alkoxy groups having 1 to 8 carbon atoms), alkylaminogroups (preferably alkylamino groups having 1 to 8 carbon atoms), anddialkylamino groups (preferably dialkylamino groups having 1 to 8 carbonatoms). Alkyl groups (preferably alkyl groups having 1 to 8 carbonatoms) and alkoxy groups (preferably alkoxy groups having 1 to 8 carbonatoms) are more preferred, and alkyl groups and alkoxy groups having 1to 4 carbon atoms are most preferred.

Examples of the compound represented by Formula (II) include compoundsrepresented by Formula (III).

Symbols in Formula (III) are each synonymous with those in Formula (II),and the preferred ranges and specific examples are also the same,provided that compounds having —NH₂ as —N(X¹R¹)X²R² are excluded.

Preferred examples of the compound represented by Formula (III) includecompounds represented by Formula (IIIa).

Symbols in Formula (IIIa) are each synonymous with those in Formula(II), and the preferred ranges are also the same, provided thatcompounds where —N(X¹R¹)X²R² is —NH₂ are excluded.

Preferred examples of the compound represented by Formula (III) includecompounds represented by Formula (IIIb).

Symbols in Formula (IIIb) are each synonymous with those in Formula(II), and the preferred ranges are also the same, provided thatcompounds where —X¹R¹ is a hydrogen atom are excluded.

Preferred examples of the compound represented by Formula (III) includecompounds represented by Formula (IIIc).

Symbols in Formula (IIIc) are each synonymous with those in Formula(II), and the preferred ranges are also the same. R⁹ represents —O—Ar,an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or aheterocyclic group, wherein Ar represents an aryl group. The aryl groupoptionally has one or more substituents.

The aryl group represented by Ar is preferably a substituted orunsubstituted phenyl or naphthyl group and more preferably a phenylgroup. The aryl group represented by Ar optionally has one or moresubstituents. Examples of the substituent include those belonging to thesubstituent group T, and preferred examples of the substituent are thesame as those possessed by R¹ or R³ in Formula (II).

Preferred examples of the compound represented by Formula (III) includecompounds represented by Formula (IIId).

Symbols in Formula (IIId) are each synonymous with those in Formula(II), and the preferred ranges are also the same.

Preferred examples of the compound represented by Formula (III) includecompounds represented by Formula (IIId-2).

Symbols in Formula (IIId-2) are each synonymous with those in Formula(II), and the preferred ranges are also the same. Q^(aa) represents asingle bond or —O—, —NH—, or —N(R)— (wherein R is an alkyl group having1 to 8 carbon atoms). R^(aa) represents a hydrogen atom, a halogen atom,or an alkyl group having 1 to 8 carbon atoms.

Preferred examples of the compound represented by Formula (III) includecompounds represented by Formula (IIIe).

Symbols in Formula (IIIe) are each synonymous with those in Formula(II), and the preferred ranges are also the same. Ar represents an arylgroup. The aryl group optionally has one or more substituents.

The aryl group represented by Ar is preferably a substituted orunsubstituted phenyl or naphthyl group and more preferably a phenylgroup. The aryl group represented by Ar optionally has one or moresubstituents. Examples of the substituent include those belonging to thesubstituent group T, and preferred examples of the substituent are thesame as those possessed by R¹ or R³ in Formula (II).

Preferred examples of the compound represented by Formula (III) includecompounds represented by Formula (IIIe-2).

Symbols in Formula (IIIe-2) are each synonymous with those in Formula(II), and the preferred ranges are also the same. Q^(aa) represents asingle bond or —O—, —NH—, or —N(R)— (wherein R is an alkyl group having1 to 8 carbon atoms). R^(aa) represents a hydrogen atom, a halogen atom,or an alkyl group having 1 to 8 carbon atoms.

In Formulae (III) to (IIIe), Q^(a) is preferably a single bond or adivalent linking group represented by —O—, —S—, —N(X^(a)—R^(h))—, or—N(X^(a)—R^(h))—X^(b)—; more preferably a single bond or —O—, —S—, —NH—,or —N(R)— (wherein R is an alkyl group having 1 to 8 carbon atoms andpreferably 1 to 4 carbon atoms); and most preferably a single bond or—O—. R^(a) is preferably a hydrogen atom, a halogen atom, an alkyl grouphaving 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms,an alkynyl group having 2 to 8 carbon atoms, an aryl group having 6 to18 carbon atoms (e.g., a benzene ring or naphthalene ring group), aheterocyclic group having 4 to 10 carbon atoms (e.g., a pyrrolyl group,a pyrrolidino group, a pyrazolyl group, a pyrazolidino group, animidazolyl group, a piperazino group, or a morpholino group); morepreferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms;and most preferably an alkyl group having 1 to 4 carbon atoms. The alkylgroup may be substituted, but is preferably unsubstituted. Examples ofthe substituent include a hydroxyl group, a cyano group, alkoxy groups,alkoxycarbonyl groups, and an amino group. When Q^(a) is —N(R)—, R^(a)is optionally bonded to R to form a ring (e.g., 5- or 6-membered ring).

Preferred examples of -Q^(a)-R^(a) include —Cl, —CH₃, -(t)C₄H₉, —OH,—OCH₃, —OC₂H₅, —NHCH₃, NHC₂H₅, —NHC₃H₇, —NHC₄H₉, —N(CH₃)₂, and—N(C₂H₅)₂. In particular, —Cl, —CH₃, —OH, —OCH₃, —NHCH₃, and NHC₂H₅ arepreferred.

Preferred examples of the compound represented by Formula (III) includecompounds represented by Formulae (IIIf) to (IIIh).

In Formula (IIIf), R^(a7) represents an alkyl group having 1 to 8 carbonatoms; and R⁶, R⁷, and R⁸ each independently represent a hydrogen atom,a halogen atom, a nitro group, a cyano group, a carbamoyl group, anN-alkylcarbamoyl group having 1 to 8 carbon atoms, anN,N-dialkylcarbamoyl group having 1 to 16 carbon atoms, a sulfamoylgroup, an N-alkylsulfamoyl group having 1 to 8 carbon atoms, anN,N-dialkylsulfamoyl group having 1 to 16 carbon atoms, an alkyl grouphaving 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbonatoms, an alkylamino group having 1 to 16 carbon atoms, a dialkylaminogroup having 1 to 16 carbon atoms, or an alkoxyalkyloxy group having 1to 16 carbon atoms.

Symbols in Formula (IIIg) are each synonymous with those in Formula(IIIf), and the preferred ranges are also the same.

Symbols in Formula (IIIh) are each synonymous with those in Formula(IIIf), and the preferred ranges are also the same.

Examples of the compound represented by Formula (II) include compoundsrepresented by Formula (IV).

Symbols in Formula (IV) are each synonymous with those in Formula (I),and the preferred ranges and specific examples are also the same,provided that compounds where —N(X¹R¹) X²R² and -Q^(a)-R^(a) are —NH₂are excluded.

Preferred examples of the compound represented by Formula (IV) includecompounds represented by Formula (IVa).

Symbols in Formula (IVa) are each synonymous with those in Formula (II),and the preferred ranges are also the same, provided that compoundswhere —N(X¹R¹)X²R² and -Q^(a)-R^(a) are —NH₂ are excluded.

Preferred examples of the compound represented by Formula (IV) includecompounds represented by Formula (IVb).

Symbols in Formula (IVb) are each synonymous with those in Formula (II),and the preferred ranges are also the same, provided that compoundswhere —X¹R¹ is a hydrogen atom and -Q^(a)-R^(a) is —NH₂ are excluded.

Preferred examples of the compound represented by Formula (IV) includecompounds represented by Formula (IVc).

Symbols in Formula (IVc) are each synonymous with those in Formula (II),and the preferred ranges are also the same. R⁹ represents —O—Ar, analkyl group, an alkenyl group, an alkynyl group, an aryl group, or aheterocyclic group, wherein Ar represents an aryl group. The aryl groupis the same as those represented by Ar in Formula (IIIc), and examplesof the substituent of the aryl group are the same.

Preferred examples of the compound represented by Formula (IV) includecompounds represented by Formula (IVd).

Symbols in Formula (IVd) are each synonymous with those in Formula (II),and the preferred ranges are also the same, provided that compoundswhere -Q^(a)-R^(a) is —NH₂ are excluded.

Preferred examples of the compound represented by Formula (IV) includecompounds represented by Formula (IVd-2).

Symbols in Formula (IVd-2) are each synonymous with those in Formula(II), and the preferred ranges are also the same. Q^(aa) represents asingle bond or —O—, —NH—, or —N(R)— (wherein R is an alkyl group having1 to 8 carbon atoms). R^(aa) represents a hydrogen atom, a halogen atom,or an alkyl group having 1 to 8 carbon atoms.

Preferred examples of the compound represented by Formula (IV) includecompounds represented by Formula (IVe).

Symbols in Formula (IVe) are each synonymous with those in Formula (II),and the preferred ranges are also the same. Ar represents an aryl group.The aryl group is the same as those represented by Ar in Formula (IIIe),and examples of the substituent of the aryl group are also the same.Compounds where -Q^(a)-R^(a) is —NH₂ are excluded.

Preferred examples of the compound represented by Formula (IV) includecompounds represented by Formula (IVe-2).

Symbols in Formula (IVe-2) are each synonymous with those in Formulae(II) and (IVd-2), and the preferred ranges are also the same. Q^(aa)represents a single bond or —O—, —NH—, or —N(R)— (wherein R is an alkylgroup having 1 to 8 carbon atoms). R^(aa) represents a hydrogen atom, ahalogen atom, or an alkyl group having 1 to 8 carbon atoms.

Preferred examples of Q^(a), R^(a), and -Q^(a)-R^(a) in Formulae (IV) to(IVe) are the same as those in Formulae (III) to (IIIe).

Preferred examples of the compound represented by Formula (IV) includecompounds represented by Formulae (IVf) to (IVh).

Symbols in Formula (IVf) are each synonymous with those in Formula(IIIf), and the preferred ranges are also the same. R^(a7) represents analkyl group having 1 to 8 carbon atoms.

Symbols in Formula (IVg) are each synonymous with those in Formula(IIIf), and the preferred ranges are also the same. R^(a7) represents analkyl group having 1 to 8 carbon atoms.

Symbols in Formula (IVh) are each synonymous with those in Formula(IIIf), and the preferred ranges are also the same. R^(a7) represents analkyl group having 1 to 8 carbon atoms.

Preferred examples of the compound represented by Formula (II) includecompounds represented by Formula (V).

Symbols in Formula (V) are each synonymous with those in Formula (II),and the preferred ranges and specific examples are also the same.

Preferred examples of the compound represented by Formula (V) includecompounds represented by Formula (Va).

Symbols in Formula (Va) are each synonymous with those in Formula (II),and the preferred ranges are also the same.

Preferred examples of the compound represented by Formula (V) includecompounds represented by Formula (Vb).

Symbols in Formula (Vb) are each synonymous with those in Formula (II),and the preferred ranges are also the same.

Preferred examples of the compound represented by Formula (V) includecompounds represented by Formula (Vc).

Symbols in Formula (Vc) are each synonymous with those in Formula (II),and the preferred ranges are also the same. R⁹ represents —O—Ar, analkyl group, an alkenyl group, an alkynyl group, an aryl group, or aheterocyclic group, wherein Ar represents an aryl group. The aryl groupis the same as those represented by Ar in Formula (IIIc), and examplesof the substituent of the aryl group are the same.

Preferred examples of the compound represented by Formula (V) includecompounds represented by Formula (Vd).

Symbols in Formula (Vd) are each synonymous with those in Formula (II),and the preferred ranges are also the same.

Preferred examples of the compound represented by Formula (V) includecompounds represented by Formula (Ve).

Symbols in Formula (Ve) are each synonymous with those in Formula (II),and the preferred ranges are also the same. Ar represents an aryl group.The aryl group is the same as those represented by Ar in Formula (IIIe),and examples of the substituent of the aryl group are the same.Compounds where -Q^(a)-R^(a) is —NH₂ are excluded.

Preferred examples of Q^(a), R^(a), and -Q^(a)-R^(a) in Formulae (V) to(Ve) are the same as those in Formulae (III) to (IIIe).

Preferred examples of the compound represented by Formula (V) includecompounds represented by Formula (Vf).

Symbols in Formula (Vf) are each synonymous with those in Formula(IIIf), and the preferred ranges are also the same.

Preferred examples of the compound represented by Formula (V) includecompounds represented by Formula (Vf′).

In Formula (Vf′), R¹¹, R¹², and R¹³ each independently represent ahydrogen atom, a nitro group, a carbamoyl group, an N-alkylcarbamoylgroup having 1 to 8 carbon atoms, an N,N-dialkylcarbamoyl group having 1to 16 carbon atoms, a sulfamoyl group, an N-alkylsulfamoyl group having1 to 8 carbon atoms, an N,N-dialkylsulfamoyl group having 1 to 16 carbonatoms, an alkyl group having 1 to 16 carbon atoms, an alkoxy grouphaving 1 to 16 carbon atoms, an alkylamino group having 1 to 16 carbonatoms, a dialkylamino group having 1 to 16 carbon atoms, or analkoxyalkyloxy group having 1 to 16 carbon atoms, provided that at leastone of R¹¹, R¹², and R¹³ represents a substituent other than a hydrogenatom.

The compounds represented by Formulae (I), (II), (III) to (IIIh), (IV)to (IVh), and (V) to (Vf′) are preferably used in application that needsrelatively low Re and Rth. In addition, polymer films containing thesecompounds and thereby having controlled Re and/or Rth are characterizedby further reduced fluctuations in Re and/or Rth depending on humidity.

Furthermore, in the present invention, a mixture of a compoundrepresented by any one of Formulae (I), (II), (III) to (IIIh), (IV) to(IVh), and (V) to (Vf′) and a compound represented by Formula (6)(preferably Formula (7)) shown below may be directly used as an additivefor polymer films. The use of a mixture of a compound represented by anyone of Formulae (I), (II), (III) to (IIIh), (IV) to (IVh), and (V) to(Vf′) and a compound represented by Formula (6) is preferred, becausethe compounds can synergistically enhance the effect of achievingretardation and the effect of reducing humidity dependency.

Ar¹ and Ar² in Formula (6) each independently represent a substituted orunsubstituted aryl group and are each synonymous with Ar in Formulae(IIIe) to (Ve), and preferred examples thereof are also the same. R¹¹ toR¹⁴ in Formula (7) each independently represent a hydrogen atom, ahalogen atom, a nitro group, a cyano group, a carbamoyl group, anN-alkylcarbamoyl group having 1 to 8 carbon atoms, anN,N-dialkylcarbamoyl group having 1 to 16 carbon atoms, a sulfamoylgroup, an N-alkylsulfamoyl group having 1 to 8 carbon atoms, anN,N-dialkylsulfamoyl group having 1 to 16 carbon atoms, an alkyl grouphaving 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbonatoms, an alkylamino group having 1 to 16 carbon atoms, a dialkylaminogroup having 1 to 16 carbon atoms, or an alkoxyalkyloxy group having 1to 16 carbon atoms and are synonymous with R⁶ to R⁸ in Formulae (IIIe)to (Ve) and preferred examples thereof are also the same.

Symbols in the formulae are each synonymous with those in Formula (I),and the preferred ranges and preferred examples are also the same.

The compounds represented by Formulae (I), (II), (III) to (IIIh), (IV)to (IVh), and (V) to (Vf′) may be used alone or in the form of a mixtureof two or more. For example, a mixture of a compound having a partialstructure (x) and a compound having a partial structure (y) shown belowmay be prepared as a product depending on the synthetic process. Such amixture can be directly used in various purposes, such as an additivefor polymer films. In addition, a compound having the above-describedpartial structure (a) may be simultaneously prepared, and the mixturecontaining the compound having the partial structure (a) prepared as aproduct can be used in various purposes, such as an additive for polymerfilms. In Formulae below, symbol * indicates a position into which anatom or a residue can be introduced.

Specific examples of the compound represented by Formulae (I) and (II)are shown below, but the compounds that can be used in the presentinvention should not be limited to the following specific examples.

[Chem. 141]

Compound No. Y Z —Q^(a)—R^(a) R^(c) Ib-1 N CH H H Ib-2 N CH H o-Me Ib-3N CH H m-Me Ib-4 N CH H p-Me Ib-5 N CH H p-t-Butyl Ib-6 N CH H o-OMeIb-7 N CH H m-OMe Ib-8 N CH H p-OMe Ib-9 N CH Me H Ib-10 N CH Me o-MeIb-11 N CH Me m-Me Ib-12 N CH Me p-Me Ib-13 N CH Me p-t-Butyl Ib-14 N CHMe o-OMe Ib-15 N CH Me m-OMe Ib-16 N CH Me p-OMe Ib-17 N CH t-Butyl HIb-18 N CH t-Butyl o-Me Ib-19 N CH t-Butyl m-Me Ib-20 N CH t-Butyl p-MeIb-21 N CH t-Butyl p-t-Butyl Ib-22 N CH t-Butyl o-OMe Ib-23 N CH t-Butylm-OMe Ib-24 N CH t-Butyl p-OMe Ib-25 N CH OMe H Ib-26 N CH OMe o-MeIb-27 N CH OMe m-Me Ib-28 N CH OMe p-Me Ib-29 N CH OMe p-t-Butyl Ib-30 NCH OMe o-OMe Ib-31 N CH OMe m-OMe Ib-32 N CH OMe p-OMe Ib-33 N CH OEt HIb-34 N CH OEt o-Me Ib-35 N CH OEt m-Me Ib-36 N CH OEt p-Me Ib-37 N CHOEt p-t-Butyl Ib-38 N CH OEt o-OMe Ib-39 N CH OEt m-OMe Ib-40 N CH OEtp-OMe Ib-41 N CH OC₂H₂OEt H Ib-42 N CH OC₂H₂OEt o-Me Ib-43 N CH OC₂H₂OEtm-Me Ib-44 N CH OC₂H₂OEt p-Me Ib-45 N CH OC₂H₂OEt p-t-Butyl Ib-46 N CHOC₂H₂OEt o-OMe Ib-47 N CH OC₂H₂OEt m-OMe Ib-48 N CH OC₂H₂OEt p-OMe Ib-49N CH NHMe H Ib-50 N CH NHMe o-Me Ib-51 N CH NHMe m-Me Ib-52 N CH NHMep-Me Ib-53 N CH NHMe p-t-Butyl Ib-54 N CH NHMe o-OMe Ib-55 N CH NHMem-OMe Ib-56 N CH NHMe p-OMe Ib-57 N CH NHEt H Ib-58 N CH NHEt o-Me Ib-59N CH NHEt m-Me Ib-60 N CH NHEt p-Me [Chem. 142]

Compound No. Y Z —Q^(a)—R^(a) R^(c) Ib-61 N CH NHEt p-t-Butyl Ib-62 N CHNHEt o-OMe Ib-63 N CH NHEt m-OMe Ib-64 N CH NHEt p-OMe Ib-65 N CH NMe₂ HIb-66 N CH NMe₂ o-Me Ib-67 N CH NMe₂ m-Me Ib-68 N CH NMe₂ p-Me Ib-69 NCH NMe₂ p-t-Butyl Ib-70 N CH NMe₂ o-OMe Ib-71 N CH NMe₂ m-OMe Ib-72 N CHNMe₂ p-OMe Ib-73 N CH

H Ib-74 N CH C₆H₅ H Ib-75 N CH OH H Ib-76 CH N H H Ib-77 CH N H o-MeIb-78 CH N H m-Me Ib-79 CH N H p-Me Ib-80 CH N H p-t-Butyl Ib-81 CH N Ho-OMe Ib-82 CH N H m-OMe Ib-83 CH N H p-OMe Ib-84 CH N Me H Ib-85 CH NMe o-Me Ib-86 CH N Me m-Me Ib-87 CH N Me p-Me Ib-88 CH N Me p-t-ButylIb-89 CH N Me o-OMe Ib-90 CH N Me m-OMe Ib-91 CH N Me p-OMe Ib-92 CH Nt-Butyl H Ib-93 CH N t-Butyl o-Me Ib-94 CH N t-Butyl m-Me Ib-95 CH Nt-Butyl p-Me Ib-96 CH N t-Butyl p-t-Butyl Ib-97 CH N t-Butyl o-OMe Ib-98CH N t-Butyl m-OMe Ib-99 CH N t-Butyl p-OMe Ib-100 CH N OMe H Ib-101 CHN OMe o-Me Ib-102 CH N OMe m-Me Ib-103 CH N OMe p-Me Ib-104 CH N OMep-t-Butyl Ib-105 CH N OMe o-OMe Ib-106 CH N OMe m-OMe Ib-107 CH N OEtp-OMe Ib-108 CH N OEt H Ib-109 CH N OEt o-Me Ib-110 CH N OEt m-Me Ib-111CH N OEt p-Me Ib-112 CH N OEt p-t-Butyl Ib-113 CH N OEt o-OMe Ib-114 CHN OEt m-OMe Ib-115 CH N OC₂H₂OEt p-OMe Ib-116 CH N OC₂H₂OEt H Ib-117 CHN OC₂H₂OEt o-Me Ib-118 CH N OC₂H₂OEt m-Me Ib-119 CH N OC₂H₂OEt p-MeIb-120 CH N OC₂H₂OEt p-t-Butyl [Chem. 143]

Compound No. Y Z —Q^(a)—R^(a) R^(c) Ib-121 CH N OC₂H₂OEt o-OMe Ib-122 CHN OC₂H₂OEt m-OMe Ib-123 CH N OC₂H₂OEt p-OMe Ib-124 CH N NHMe H Ib-125 CHN NHMe o-Me Ib-126 CH N NHMe m-Me Ib-127 CH N NHMe p-Me Ib-128 CH N NHMep-t-Butyl Ib-129 CH N NHMe o-OMe Ib-130 CH N NHMe m-OMe Ib-131 CH N NHMep-OMe Ib-132 CH N NHEt H Ib-133 CH N NHEt o-Me Ib-134 CH N NHEt m-MeIb-135 CH N NHEt p-Me Ib-136 CH N NHEt p-t-Butyl Ib-137 CH N NHEt o-OMeIb-138 CH N NHEt m-OMe Ib-139 CH N NHEt p-OMe Ib-140 CH N NMe₂ H Ib-141CH N NMe₂ o-Me Ib-142 CH N NMe₂ m-Me Ib-143 CH N NMe₂ p-Me Ib-144 CH NNMe₂ p-t-Butyl Ib-145 CH N NMe₂ o-OMe Ib-146 CH N NMe₂ m-OMe Ib-147 CH NNMe₂ p-OMe Ib-148 CH N

H Ib-149 CH N C₆H₅ H Ib-150 CH N OH H Ib-151 CH CH H H Ib-152 CH CH Ho-Me Ib-153 CH CH H m-Me Ib-154 CH CH H p-Me Ib-155 CH CH H p-t-ButylIb-156 CH CH H o-OMe Ib-157 CH CH H m-OMe Ib-158 CH CH H p-OMe Ib-159 NCH Cl H Ib-160 N CH Cl m-Me Ib-161 CH N Cl H lb-162 CH N Cl m-Me [Chem.144]

Compound No. Y Z —Q^(a) —R^(a) —X¹—R¹ —X²—R² IIb-1 N CH OH

H IIb-2 N CH Cl COOMe H IIb-3 N CH Cl

H IIb-4 N CH H

H IIb-5 N CH CH₃ C₅H₁₁ H IIb-6 N CH

H IIb-7 CH N Cl

H IIb-8 CH N Cl

H IIb-9 CH N CH₃

H IIb-10 CH N

CH₃ H IIb-11 CH N C₆H₅ C₆H₅ H IIb-12 N CH OCH₃ CH₃ CH₃ IIb-13 N CH CH₃CH₃ C₆H₅ IIb-14 CH N CH₃ CH₃ CH₃ IIb-15 CH N CH₃ CH₃ C₆H₅ IIb-16 CH CH H

H IIb-17 CH CH H COCH₃

IIb-18 CH CH H H

IIb-19 CH CH H H

IIb-20 CH CH

H

IIb-21 N CH H —OC₆H₅ H IIb-22 CH N CH₃ —OC₆H₅ H [Chem. 145]

Compound No. —Q^(b)—R^(b) —Q^(a)—R^(a) —X¹—R¹ IIIb-1 SMe

IIIb-2

H

IIIb-3

H

IIIb-4

Ethyl

IIIb-5

Ethyl

IIIb-6 —(CH₂)₄—

[Chem. 146]

Compound No. —Q^(d)—R^(d) —Q^(a)—R^(a) —X¹—R¹ IVb-1

CH₃ COCH₃ IVb-2 OH CH₃

IVb-3 —(CH₂)₄—

In the following, both compound groups A and B will be described.Hereinafter, the “compound of Formula (0)” and the “inventive compound”should include both compound groups A and B.

The scope of the present invention includes polymer films in which thecompounds represented by Formula (0) are added in the form of hydratesof the compounds, solvates of the compounds, or salts of the compound.In the present invention, the hydrate may contain an organic solvent,and the solvate may contain water. That is, the terms “hydrate” and“solvate” should include a solvate mixture containing water and anorganic solvent. As described above, a hydrate of the compound, solvateof the compound, and salt of the compound are preferred in theembodiments of solvent-casting method.

The film that the compounds represented by Formula (0) are added in theform of hydrates of the compounds, solvates of the compounds, or saltsof the compounds may not maintain the hydrate of the compound, solvateof the compound, or salt of the compound in the film. Even in such acase, the film-forming stability that is provided by the compound in theform such as a hydrate contributes to stabilization of the content ofthe compound represented by Formula (0) in the resulting film, a reducedvariation in optical characteristics of the film, and a reduction independency of optical characteristics on environmental humidity.

Examples of the salt include acid addition salts formed with inorganicor organic acids. Examples of the inorganic acid include, but are notlimited to, hydrohalic acids (such as hydrochloric acid and hydrobromicacid), sulfuric acid, and phosphoric acid. Examples of the organic acidinclude, but are not limited to, acetic acid, trifluoroacetic acid,oxalic acid, citric acid, benzoic acid, alkyl sulfonic acids (such asmethanesulfonic acid), and allylsulfonic acids (benzenesulfonic acid,4-toluenesulfonic acid, 1,5-naphthalenedisulfonic acid). Among them,hydrochlorides and acetates are preferred. Examples of the salt alsoinclude, but are not limited to, salts formed by substitution of acidicmoieties of parent compounds with metal ions (e.g., alkali metal saltssuch as sodium and potassium salts, alkaline earth metal salts such ascalcium and magnesium salts, ammonium salts, alkali metal ions, alkalineearth metal ions, and aluminum ions or formed through preparation withorganic bases (such as ethanolamine, diethanolamine, triethanolamine,morpholine, and piperidine). In particular, sodium salts and potassiumsalts are preferred.

Examples of the solvent contained in a solvate include organic solventsthat are usually used. Specific examples thereof include alcohols (e.g.,methanol, ethanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, andt-butanol), esters (e.g., ethyl acetate), hydrocarbons (e.g., toluene,hexane, and heptane), ethers (e.g., tetrahydrofuran), nitriles (e.g.,acetonitrile), and ketones (e.g., acetone and 2-butanone). Preferredexamples are solvates of alcohols (e.g., methanol, ethanol, 2-propanol,1-butanol, 1-methoxy-2-propanol, and t-butanol), and more preferredexamples are methanol, ethanol, 2-propanol, and 1-butanol. Thesesolvents may be reaction solvents that are used in synthesis of thecompounds or solvents that are used in crystallization purificationafter synthesis or may be mixtures thereof.

In addition, the solvate may contain two or more solvents or may containwater and a solvent (e.g., water and alcohol (such as methanol, ethanol,or t-butanol)).

The inventive compound may be in a hydrate, solvate, or solvate mixtureform in which the compound and water and/or a solvent are present at acertain proportion and of which the water content ratio, solvent contentratio, or solvent mixture content ratio does not change within certainranges of temperature, humidity, and pressure. Such hydrate, solvate,and solvate mixture have specific crystal structures and show specificdiffraction patterns in powder X-ray diffraction (XRD). However, thehydrate, solvate, and solvate mixture exposed to environments, such ashigh temperature or reduced pressure, beyond the certain ranges lose thewater content ratio, solvent content ratio, or the solvent mixturecontent ratio and may be changed to amorphous forms. Herein, the term“amorphous” refers to a form not having any crystal structure ofregularly arranged molecules. The amorphous form can be prepared by, forexample, heating the compound in a hydrate, solvate, or solvate mixtureform to a temperature higher than the melting point to melt the compoundand remove the water or the solvent and then rapidly cooling thecompound. The resulting amorphous compound may be hydrated according tothe environmental humidity, and the water content ratio varies dependingon the environmental humidity. However, this hydrous amorphous compounddoes not show any diffraction pattern in powder X-ray diffraction and istherefore distinguished from the hydrate composed of the inventivecompound and water at a proportion within a certain range and of whichthe water content ratio does not change within certain ranges oftemperature, humidity, and pressure.

The inventive compound in an amorphous form not showing any powder X-raydiffraction pattern has a variable water content ratio depending on theenvironmental humidity. Accordingly, the compound is preferably used ina crystal form (anhydride, hydrate, solvate, or solvate mixture) showinga powder X-ray diffraction pattern.

The compound in the present invention in an amorphous form has avariable water content ratio depending on the environmental humidity andis therefore preferably used in a crystal form (anhydride, hydrate,and/or solvate).

Herein, the term “crystal” refers to a solid having a crystal structurecomposed of constituent atoms that are regularly and three-dimensionallyarranged. Crystals may be in the form of an anhydride, hydrate, and/orsolvate and usually have a specific crystal structure and peaks atdiffraction angles corresponding to crystal planes in a powder X-raydiffractogram. Throughout the specification, such characteristics aredescribed as “showing a diffraction pattern in a crystalline powderX-ray diffractogram”. A compound in an amorphous form usually has abroad single peak (halo) in powder X-ray diffraction. Throughout thespecification, such characteristics are described as not showing anydiffraction pattern in powder X-ray diffraction. An amorphous form and acrystalline form can also be distinguished from each other by analysissuch as thermal analysis, as well as powder X-ray diffraction.

In a hydrate, solvate, or solvate mixture form, water, a solvent, or asolvent mixture may be incorporated into the compound represented byFormula (0) at any proportion. In a hydrate or a solvate, the number ofwater and/or solvent molecules incorporated into one molecule of acompound is generally an integral multiple, however, the water and/orsolvent may also be incorporated into gaps between crystals. In such acase, the proportion is not an integral multiple.

In the hydrate or solvate of the present invention, the proportion ofthe number of water and/or solvent molecules to one molecule of thecompound is not limited, but is preferably 0.25 to 4 molecules of waterand/or solvent for one molecule of the compound.

In terms of weight, for example, a water content ratio of 0.8 to 25% ispreferred in a case of hydrate though it depends on the molecular weightof the compound.

The water content ratio of the hydrate is preferably 1% or more and morepreferably 2% or more, in particular, for reducing the variations inoptical characteristics of a film. The upper limit of the water contentratio is preferably 15% or less and more preferably 10% or less, fromthe viewpoints of solubility (in an organic solvent) and load on theproduction process. The same can apply to the solvent content ratio in asolvate.

The hydrate can be produced by crystallizing the compound from water.Since many organic solvents contain a slight amount of water,crystallization from an organic solvent also gives a hydrate having awater content ratio within the above-mentioned range. Furthermore,crystallization from an organic solvent containing a required amount ofwater can also give a hydrate having a water content ratio within theabove-mentioned range.

The compound represented by Formula (0) used in the present inventionpreferably has a molecular weight of 200 to 2000, more preferably 200 to1000, and most preferably 200 to 600.

The compound represented by Formula (0) may be produced by any method,and various methods are applicable. Nonlimiting examples of the methodwill now be described.

The compound represented by Formula (0) can be synthesized by, forexample, the process of Scheme 1-1. That is, the compound can besynthesized by a reaction of a compound of Formula (1a) with a compoundof Formula (1b) under a solvent-free condition or in an organic solvent.The groups in Formulae (1a) and (1b) are each synonymous with those inFormula (1) or (I). Z represents a leaving group and is preferably ahalogen atom (e.g., Cl, Br, or I), a hydroxyl group, an alkoxy groups(preferably C₁ to C₄ alkoxy group, more preferably C₁ to C₂ alkoxygroup, and most preferably C₁ alkoxy group), an aryloxy groups(preferably C₁ to C₈ aryloxy group), a hetero ring group, an acyloxygroups (preferably C₂ to C₈ acyloxy group), an alkylsulfonyloxy groups(preferably C₁ to C₄ alkylsulfonyloxy group), or an arylsulfonyloxygroup. In particular, a halogen atom, an alkoxy group, an aryloxy group,or an acyloxy group is preferred.

The compounds represented by Formula (1a) and Formula (1b) may becommercially available products or may be synthesized by knownprocesses. Examples of the usable organic solvent include alcohols(e.g., methanol, ethanol, 1-butanol, 1-methoxy-2-propanol, andt-butanol), esters (e.g., ethyl acetate), hydrocarbons (e.g., toluene),ethers (e.g., tetrahydrofuran), amides (e.g., dimethylformamide,dimethylacetamide, N-methylpyrrolidone, and N-ethylpyrrolidone),halogenated hydrocarbons (e.g., dichloromethane), nitriles (e.g.,acetonitrile), and solvent mixtures thereof. Among them, hydrocarbons,alcohols, and amides are preferred; and toluene, methanol, ethanol,1-methoxy-2-propanol, t-butanol, dimethylacetamide, N-methylpyrrolidone,and N-ethylpyrrolidone are particularly preferred. Solvent mixtures oftoluene, methanol, ethanol, 1-methoxy-2-propanol, t-butanol,dimethylacetamide, N-methylpyrrolidone, or N-ethylpyrrolidone are alsoparticularly preferred. A mixture of an organic solvent and water isalso preferred.

The reaction of a compound of Formula (1a) with a compound of Formula(1b) can be also preferably performed in the presence of a base. Thebase may be an inorganic base (e.g., potassium carbonate, sodiumbicarbonate, sodium hydroxide, or potassium hydroxide) or an organicbase (e.g., pyridine, triethylamine, sodium methoxide, sodium ethoxide,t-butoxy potassium, or t-butoxy sodium), and can be appropriatelyselected according to the type of Z. When Z is an alkoxy group, the baseis preferably an inorganic base, in particular, sodium methoxide. Theamount of the base is preferably in a range of 0.5 to 10 equivalents,more preferably 0.5 to 6 equivalents, to the compound represented byFormula (1b). When Z is a halogen atom, inorganic bases and organicbases are both preferable, and, for example, pyridine and sodiumbicarbonate are more preferred.

The reaction temperature is usually in a range of −20° C. to the boilingpoint of the solvent and preferably in a range of room temperature tothe boiling point of the solvent.

The reaction time ranges usually from 10 minutes to 3 days andpreferably from 1 hour to 1 day. The reaction may be performed under anitrogen atmosphere or reduced pressure. In particular, when the leavinggroup Z is an alkoxy group or an aryloxy group, the reaction is alsopreferably performed under reduced pressure.

Another example of the method of producing a compound represented byFormula (0) is shown in Scheme 1-2. That is, the compound can besynthesized by a reaction of a compound of Formula (1c) with a compoundof Formula (1d) under a solvent-free condition or in an organic solvent,in the absence of a base or in the presence of a base.

The compounds represented by Formula (1c) and Formula (1d) may becommercially available products or may be synthesized by knownprocesses. Examples of the usable organic solvent include alcohols(e.g., methanol and ethanol), esters (e.g., ethyl acetate), hydrocarbons(e.g., toluene), ethers (e.g., tetrahydrofuran), amides (e.g.,dimethylformamide, dimethylacetamide, N-methylpyrrolidone, andN-ethylpyrrolidone), halogenated hydrocarbons (e.g., dichloromethane),nitriles (e.g., acetonitrile), and solvent mixtures thereof. Alcoholsand amides are preferred; and methanol, ethanol, 1-methoxy-2-propanol,t-butanol, dimethylacetamide, N-methylpyrrolidone, andN-ethylpyrrolidone are particularly preferred. Solvent mixtures ofmethanol, ethanol, 1-methoxy-2-propanol, t-butanol, dimethylacetamide,N-methylpyrrolidone, or N-ethylpyrrolidone are also particularlypreferred.

When a base is used, the base may be an inorganic base (e.g., potassiumcarbonate) or an organic base (e.g., triethylamine, sodium methoxide, orsodium ethoxide). The inorganic base is preferred, in particular, sodiumhydroxide, sodium carbonate, and sodium bicarbonate are preferred. Theamount of the base is preferably in a range of 0.5 to 10 equivalents,more preferably 1 to 5 equivalents, to the compound represented byFormula (1c).

The reaction temperature is usually in a range of −20° C. to the boilingpoint of the solvent and preferably in a range of room temperature tothe boiling point of the solvent.

The reaction time ranges usually from 10 minutes to 3 days andpreferably from 1 hour to 1 day. The reaction may be performed under anitrogen atmosphere or reduced pressure.

The groups in Formulae (1c) and (1d) are each synonymous with those inthe formulae mentioned above. Z¹ represents a leaving group and ispreferably a halogen atom.

The compound of Formula (2)′, which is a compound belonging to thecompound group A and is an example of Formula (2), can be synthesizedby, for example, the process of Scheme 2-1. That is, the compound can besynthesized by a reaction of a compound of Formula (2a) with a compoundof Formula (1b) under a solvent-free condition or in an organic solvent,in the presence of a base. The compounds represented by Formula (2a) andFormula (1b) may be commercially available products or may besynthesized by known processes. Examples of the usable organic solventand the base are the same as those in the reactions in Schemes 1-1 and1-2; and the reaction temperature and the reaction time are also thesame as those in the above-described Schemes.

The groups in Formula (2a) are each synonymous with those in theformulae mentioned above. Formula (1b) is the same as above.

The compound of Formula (6)′, which is an example of Formula (6), can besynthesized by, for example, the process of Scheme 2. That is, thecompound can be synthesized by a reaction of a compound of Formula (6a)with a compound of Formula (6b) under a solvent-free condition or in anorganic solvent. The compounds represented by Formula (6a) and Formula(6b) may be commercially available products or may be synthesized byknown processes. The reaction of a compound of Formula (6a) with acompound of Formula (6b) can be also preferably performed in thepresence of a base. Examples of the usable organic solvent and the baseare the same as those in the reaction in Scheme 1-1; and the reactiontemperature and the reaction time are also the same as those in theabove-described Schemes.

The groups in Formulae (6a) and (6b) are each synonymous with those inFormula (6). Ar is an aryl group. Z is synonymous with that in Formula(1b). The leaving group Z is preferably a halogen atom, an alkoxy group,an aryloxy group, or an acyloxy group, more preferably an alkoxy group,more preferably a C₁ to C₄ alkoxy group, more preferably a C₁ to C₂alkoxy group, and most preferably a C₁ alkoxy group.

The compound of Formula (7-1) can be synthesized by, for example, theprocess of Scheme 3. That is, the compound can be synthesized by areaction of a compound of Formula (7a) with a compound of Formula (7b)under a solvent-free condition or in an organic solvent. The compoundsrepresented by Formula (7a) and Formula (7b) may be commerciallyavailable products or may be synthesized by known processes. Thereaction of a compound of Formula (7a) with a compound of Formula (7b)can be also preferably performed in the presence of a base. Examples ofthe usable organic solvent and the base are the same as those in thereaction in Scheme 1-1; and the reaction temperature and the reactiontime are also the same as those in the above-described Schemes.

The groups in Formulae (7a) and (7b) are each synonymous with those inFormula (7-1). Z is synonymous with that in Formula (1b) and ispreferably a halogen atom, an alkoxy group, an aryloxy group, or anacyloxy group, more preferably an alkoxy group, more preferably a C₁ toC₄ alkoxy group, more preferably a C₁ to C₂ alkoxy group, and mostpreferably a C₁ alkoxy group.

The starting material, a diaminopyrimidine compound represented byFormula (7a), may be a commercially available product or may besynthesized by a known process. Alternatively, a compound of Formula(7a) synthesized from commercially available materials may be directlyused without purification for the reaction.

Examples of the commercially available compound usable as a raw materialin the synthesis examples of Schemes 1-1, 1-2, 2, and 3 include2,4,6-trichloropyrimidine, 2-amino-4,6-dichloropyrimidine,2,4-diamino-6-chloropyrimidine, 2,4-diamino-6-hydroxypyrimidine, and2,4-diaminopyridine. The inventive compound can be synthesized fromthese materials by combining a nucleophilic substitution reaction and acondensation reaction, for example.

The compound of Formula (1) and a precursor thereof can also besynthesized by direct construction of a hetero ring (pyrimidine ring orpyridine ring) through a cyclization reaction. Thus, various knownprocesses can be employed.

The compounds of Formulae (IIIe) and (IVe), which are compoundsbelonging to the compound group B, can be synthesized by, for example,the processes of Scheme II shown below. That is, the compounds ofFormulae (IIIe) and (IVe) can be synthesized by a reaction of a compoundof Formula (IIIe-a) with a compound of Formula (IIIe-b) and a reactionof a compound of Formula (IVe-a) with a compound of Formula (IVe-b),respectively, under a solvent-free condition or in an organic solvent.The compounds represented by Formulae (IIIe-a), (IVe-a), (IIIe-b), and(IVe-b) may be commercially available products or may be synthesized byknown processes. Examples of the usable organic solvent and the base arethe same as those in the reactions in Schemes 1-1 and 1-2; and thereaction temperature and the reaction time are also the same as those inthe above-described Schemes.

The groups in Formulae (IIIe-a), (IVe-a), (IIIe-b), and (IVe-b) are eachsynonymous with those in Formulae (IIIe) and (IVe). Z is synonymous withthat in Formula (1b) and is preferably a halogen atom, an alkoxy group,an aryloxy group, or an acyloxy group, and more preferably an alkoxygroup.

The compounds of Formulae (IIIe) and (IVe) can also be synthesized by,for example, the processes of Scheme III shown below. That is, thecompounds can be synthesized by hydrolysis or solvolysis of a compoundof Formula (IIIe-c) under a solvent-free condition or in an organicsolvent in the presence of an acid or a base.

The inventive compound may be isolated by any common method and ispreferably extracted in the form of crystals by crystallization. Thecrystallization can be performed using a common organic solvent orwater. Isolation in a hydrate form by crystallization from water is alsopreferred.

(1-2) Polymer

The polymer film of the present invention contains, as a main component,one or more polymers selected from various polymer materials. Anypolymer can be used, and examples of the usable polymer include polymershaving hydroxyl groups. Examples of the hydroxyl group-containingpolymer include polyvinyl alcohol, modified products thereof, andcellulose acylate resins. The examples of the hydroxyl group-containingpolymer include derivatives in which the hydroxyl groups are substitutedby other substituents and cellulose acylate resins in which all hydroxylgroups are substituted by acyl groups.

In one embodiment, the film of the present invention contains acellulose acylate resin as the hydroxyl group-containing polymer.Cellulose has free hydroxyl groups at 2-, 3-, and 6-positions perβ-1,4-bonding glucose unit. The film in this embodiment preferablycontains the cellulose acylate resin as a main component. Herein, theterm “contain as a main component” has the following meanings: when acellulose acylate film contains a single cellulose acylate resin as thematerial of the film, the cellulose acylate resin is the main component;and when a cellulose acylate film contains multiple cellulose acylateresins, the cellulose acylate resin having the highest proportion is themain component.

The starting cellulose for the cellulose acylate includes cotton linterand wood pulp (hardwood pulp, softwood pulp), etc.; and any celluloseacylate obtained from any starting cellulose can be used herein. As thecase may be, different starting celluloses may be mixed for use herein.The starting cellulose materials are described in detail, for example,in “Plastic Material Lecture (17), Cellulosic Resin” (written byMarusawa & Uda, published by Nikkan Kogyo Shinbun, 1970), and inHatsumei Kyokai Disclosure Bulletin No. 2001-1745, pp. 7-8. Anycellulose material described in these can be used here with no specificlimitation.

The cellulose acylate resin may contain any acyl group, but are notlimited to, the acyl group is preferably an acetyl group, a propionylgroup, or a butyryl group, and more preferably an acetyl group.

Specifically, the cellulose acylate resin preferably contains celluloseacylate simultaneously satisfying the following expressions (i) to(iii):

2.0≦A+B≦3,  Expression (i):

1.0≦A≦3, and  Expression (ii):

0≦B≦1.0.  Expression (iii):

In the expressions (i) to (iii), A represents the degree of acetylsubstitution, and B represents the sum of the degree of propionylsubstitution and the degree of butyryl substitution.

The degree of acyl substitution in the cellulose acylate resin morepreferably simultaneously satisfies the following expressions (iv) to(vi):

2.0≦A+B≦3,  Expression (iv):

1.5≦A≦3, and  Expression (v):

B=0.  Expression (vi):

In the expressions (iv) to (vi), A represents the degree of acetylsubstitution, and B represents the sum of the degree of propionylsubstitution and the degree of butyryl substitution.

The degree of acetyl substitution, the degree of propionyl substitution,and the degree of butyryl substitution in a cellulose acylate resinrespectively mean the proportions of acetylation and propionylationand/or butyrylation of three hydroxyl groups of a constituent unit((β)-1,4-glycoside bonding glucose) of cellulose. Throughout thespecification, the degrees of acetyl substitution, propionylsubstitution, and butyryl substitution of a cellulose acylate resin canbe calculated from the observed amount of the bonding fatty acid per theconstituent unit mass of cellulose. The measurement is performed inaccordance with “ASTM D817-91”.

The cellulose acylate resin preferably has a degree of polymerization of350 to 800 and more preferably 370 to 600. The cellulose acylate resinused in the present invention preferably has a number-average molecularweight of 70000 to 230000, more preferably 75000 to 230000, and mostpreferably 78000 to 120000.

The cellulose acylate resin can be synthesized using an acid anhydrideor an acid chloride as the acylating agent. A most common synthesis onan industrial scale is as follows: Cellulose obtained from cotton linteror wood pulp is esterified with a mixed organic acid componentcontaining organic acids (acetic acid, propionic acid, and butyric acid)corresponding to the acetyl group and the propionyl group and/or thebutyryl group or acid anhydrides thereof (acetic anhydride, propionicanhydride, and butyric anhydride) to synthesize an intended celluloseacylate resin.

(1-3) Amount of Inventive Compound

The amount of a compound represented by Formula (1), i.e., a compoundbelonging to the compound group A, in a film of the present invention ispreferably 30 parts by mass or less, more preferably 0.01 to 30 parts bymass, more preferably 0.01 to 20 parts by mass, and most preferably 0.1to 15 parts by mass, based on 100 parts by mass of the main polymercomponent (e.g., a hydroxyl group-containing polymer).

The total content of additives (optionally including another additivetogether with the compound represented by Formula (1)) contained in thefilm of the present invention is preferably 55% by mass or less, morepreferably 35% by mass or less, more preferably 30% by mass or less, andmost preferably 20% by mass or less, based on 100 parts by mass of themain polymer component.

The compounds represented by Formula (1) may be used alone or incombination of two or more. A reaction mixture produced using two ormore compounds represented by Formula (1b) or Formula (7b) in theprocess of Scheme 2-1 or 3-1 can be preferably used.

When two or more compounds represented by Formula (1) are used asdescribed above, it is preferable that the total amount of the compoundsrepresented by Formula (1) be within the preferred range mentionedabove.

The compound represented by Formula (1) may be prepared in the form of ahydrate of the compound or a solvate of the compound, and such a hydrateor solvate may be directly used or may be used after removal of water orthe solvent. If the water or the solvent of crystals prepared in theform of a hydrate or a solvate has been removed once, the content of thecompound may vary by, for example, moisture adsorption. Accordingly,direct use of the crystals prepared in the form of a hydrate or asolvate is more preferred.

The amount of a compound represented by Formula (I), i.e., a compoundbelonging to the compound group B, in a film of the present invention ispreferably 30 parts by mass or less, more preferably 0.01 to 30 parts bymass, more preferably 0.01 to 20 parts by mass, and most preferably 0.01to 15 parts by mass, based on 100 parts by mass of the main polymercomponent (e.g., a hydroxyl group-containing polymer). In order toachieve higher Re and Rth in the use of the compound together with acompound represented by Formula (6) belonging to the compound group A,as described below, the amount of the inventive compound is preferablyless than that of the compound of Formula (6). In such an embodiment,the amount of the compound represented by Formula (I) is preferably0.001 to 5% by mass, more preferably 0.001 to 2% by mass, and mostpreferably 0.001 to 1% by mass, based on 100 parts by mass of the mainpolymer component.

The total content of additives (optionally including another additivetogether with the compound represented by Formula (I)) contained in thefilm of the present invention is preferably 55% by mass or less, morepreferably 35% by mass or less, more preferably 30% by mass or less, andmost preferably 20% by mass or less, based on 100 parts by mass of themain polymer component.

The compounds represented by Formula (I) may be used alone or incombination of two or more. A reaction mixture produced using two ormore compounds represented by Formula (1b) or Formula (7b) in theprocess of Scheme 2-1 or 3-1 can be preferably used.

When two or more compounds represented by Formula (I) are used asdescribed above, the total amount of the compounds represented byFormula (I) is within the preferred range mentioned above.

The compound represented by Formula (I) may be prepared in the form of ahydrate or a solvate, and such a hydrate or solvate may be directly usedor may be used after removal of water or the solvent. If the water orthe solvent of crystals prepared in the form of a hydrate or a solvatehas been removed once, the content of the compound may vary by, forexample, moisture adsorption. Accordingly, direct use of the crystalsprepared in the form of a hydrate or solvate is more preferred.

As described above, in the present invention, a mixture of a compoundrepresented by any of Formulae (I), (II), (III) to (IIIh), (IV) to(IVh), and (V) to (Vf′) belonging to the compound group B and a compoundrepresented by Formula (6) (preferably Formula (7)) belonging to thecompound group A may be directly used as an additive for a polymer film.In this embodiment, the compound represented by any of Formulae (I),(II), (III) to (IIIh), (IV) to (IVh), and (V) to (Vf′) and the compoundrepresented by Formula (6) (preferably Formula (7)) may be mixed at anyproportion (when each compound is a mixture of two or more compoundsrepresented by any of Formulae (I), (II), (III) to (IIIh), (IV) to(IVh), and (V) to (Vf′) or represented by Formula (6) (preferablyFormula (7)), where the proportion is based on the total amount of thecompounds). A higher proportion of the compound represented by Formula(6) (preferably Formula (7)) enhances the achievement of Re and Rth andis useful in application in which higher Re and Rth are preferred. Onthe contrary, a higher proportion of the compound represented by aformula according to the present invention such as Formula (I) is usefulin application in which relatively low Re and Rth are preferred. In theformer application, the proportion of the compound represented by aformula according to the present invention such as Formula (I) to thecompound represented by Formula (6) (preferably Formula (7)) rangespreferably from 0.01 to 5% by mass, more preferably from 0.01 to 3% bymass, and most preferably from 0.01 to 2% by mass. In the latterembodiment, the proportion of the compound represented by Formula (6)(preferably Formula (7)) to the compound represented by a formulaaccording to the present invention such as Formula (I) ranges preferablyfrom 50% by mass or less, more preferably from 20% by mass or less, andmost preferably from 10% by mass or less.

(1-4) Other Additives

The polymer film of the present invention may further contain anadditive depending on the purpose, in addition to the compoundrepresented by Formula (0). When the polymer film is produced by asolution-casting method, such an additive can be added to polymer resindope, such as a cellulose acylate dope, at any timing. The additive isselected from agents that compatible (soluble in cellulose acylate dopein liquid film forming) with polymers (e.g., cellulose acylate). Theadditive is compounded to the polymer film for controlling the opticaland other characteristics.

A polymer film according to an embodiment of the present inventioncontains a compound represented by Formula (1) belonging to the compoundgroup A and at least one compound represented by any one of Formula(IIIe), (IVe), and (Ve) belonging to the compound group B. Symbols inthese formulae are synonymous with those in formulae mentioned above,and the preferred ranges and preferred examples are also the same. Arrepresents an aryl group and is synonymous with Ar¹ in Formula (5-1),and the preferred ranges are the same.

These compounds may be obtained as by-products during synthesis of thecompound represented by Formula (6).

The proportion of the amount of the compounds (IIIe), (IVe), and (Ve) tothe compound represented by Formula (1) ranges preferably from 5% bymass or less, more preferably from 3% by mass or less, and mostpreferably from 2% by mass or less. The lower limit of each proportionof the compounds (IIIe), (IVe), and (Ve) is, for example, 0.01% by massor more. In another embodiment, the polymer film may not contain thecompounds (IIIe), (IVe), and (Ve).

The amount of the compounds (IIIe), (IVe), and (Ve) contained in thefilm of this embodiment is preferably 5 parts by mass or less, morepreferably 2.5 parts by mass or less, and most preferably 1.5 parts bymass or less.

Specific examples of the compound represented by Formula (IIIe), (IVe),or (Ve) that is preferably used together with a compound belonging tothe compound group A and specific examples of the combination of acompound of Formula (1) belonging to the compound group A and a compoundrepresented by Formula (IIIe), (IVe), or (Ve) belonging to the compoundgroup B are shown, but not limited thereto, below.

[Chem. 155]

Compound No. Y Z —Q^(a)—R^(a) R ^(c) M-1a N CH CH₃ H M-2a CH N CH₃ HM-3a N CH CH₃ m-CH₃ M-4a CH N CH₃ m-CH₃ M-5a N CH OCH₃ H M-6a CH N OCH₃H M-7a N CH OCH₃ m-CH₃ M-8a CH N OCH₃ m-CH₃ M-9a N CH Cl H M-10a CH N ClH M-11a N CH NHCH₃ m-CH₃ M-12a CH N NHCH₃ m-CH₃ M-13a CH CH H H M-14a CHCH H m-CH₃

TABLE 1 Formula(IIIe) or Formula(1) Formula(Ve) Formula(IVe) AmountAmount Amount Mixture (% by (% by (% by No. Material mass) Materialmass) Material mass) R-1  (1-2)  95 M-1a  2.5 M-2a  2.5 R-2  (1-9)  95M-5a  2.5 M-6a  2.5 R-3  (1-9)  96 M-5a  2 M-6a  2 R-4  (1-9)  97.5M-5a  2.5 M-6a  0 R-5  (1-9)  97.5 M-5a  0 M-6a  2.5 R-6  (1-9)  98M-5a  1 M-6a  1 R-7  (1-9)  99.5 M-5a  0.1 M-6a  0.4 R-8  (2-2)  96M-3a  2 M-4a  2 R-9  (2-2)  95 M-3a  2 M-4a  3 R-10 (2-2)  95 M-3a  0M-4a  5 R-11 (2-2)  98.5 M-3a  0.5 M-4a  1 R-12 (2-2)  99.5 M-3a  0.1M-4a  0.4 R-13 (2-2)  99.8 M-3a  0 M-4a  0.2 R-14 (6-16) 98 M-9a  0M-10a 2 R-15 (7-1)  95 M-13a 5 — —

(Plasticizer)

The polymer film of the present invention preferably contains aplasticizer for improving, for example, the film-forming properties. Useof a saccharide plasticizer selected from a compound group consisting ofsaccharides and derivatives thereof or an oligomer plasticizer selectedfrom oligomers including polycondensation esters of dicarboxylic acidsand diols and derivatives thereof preferably improves the environmentalhumidity resistance of polymer films. Specifically, the use can reducethe fluctuation in Rth depending on humidity. The effect of reducing thefluctuation in Rth depending on humidity is further enhanced by acombined use of the saccharide plasticizer and the oligomer plasticizer.

(Saccharide Plasticizer)

As described above, the polymer film of the present invention preferablycontains at least one compound selected from the compound groupconsisting of saccharides and derivatives thereof. In particular, acompound selected from the compound group consisting of mono- todeca-saccharides and derivatives thereof is a preferred plasticizer.Examples of such a compound include sugar derivatives in which a part orall of hydrogen atoms of hydroxyl groups of sugars such as glucose aresubstituted by acyl groups described in paragraphs [0042] to [0065] ofInternational Publication No. WO2007/125764. The amount of thesaccharide plasticizer is preferably 0.1% by mass or more and less than20% by mass, more preferably 0.1% by mass or more and less than 10% bymass, and most preferably 0.1% by mass or more and less than 7% by massbased on the amount of the main polymer component (e.g., celluloseacylate).

(Oligomer Plasticizer)

As described above, the polymer film of the present invention preferablycontains an oligomer plasticizer selected from the oligomers. Preferredexamples of the oligomer plasticizer include polycondensation esters ofa diol component and a dicarboxylic acid compound and derivativesthereof (hereinafter also referred to as “polycondensation ester basedplasticizer”); and oligomers of methyl acrylate (MA) and derivativesthereof (hereinafter also referred to as “MA oligomer plasticizer”).

The polycondensation ester is a polycondensation ester of a dicarboxylicacid ingredient and a diol ingredient. The dicarboxylic acid ingredientmay consist of one dicarboxylic acid or any mixture of two or moredicarboxylic acids. Among these, the dicarboxylic acid ingredientcontaining at least one aromatic dicarboxylic acid and at least onealiphatic dicarboxylic acid is preferable. As well as the dicarboxylicacid ingredient, the diol ingredient may consist of one diol or anymixture of two or more diols. Among these, as the diol ingredient,ethylene glycol and/or aliphatic diol having the averaged number ofcarbon atoms of more than 2 and not more than 3.0 is preferable.

Regarding the ratio of the aromatic dicarboxylic acid to the aliphaticdicarboxylic acid contained in the dicarboxylic acid ingredient, theratio of the aromatic dicarboxylic acid is preferably from 5 to 70 mol%. In the case that the ratio falls within the range, it is possible toreduce the environmental humidity-dependence and to prevent thebleeding-out from generating in the film formation process. The ratio ofthe aromatic dicarboxylic acid in the dicarboxylic acid ingredient ismore preferably from 10 to 60 mol %, and even more preferably from 20 to50 mol %.

Examples of the aromatic dicarboxylic acid include phthalic acid,terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid,1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid,2,8-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid andthe like are preferably used, and phthalic acid and terephthalic acidare more preferred. Examples of the aliphatic dicarboxylic acid that ispreferably used in the present invention include oxalic acid, malonicacid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipicacid, pimelic acid, suberic acid, azelaic acid, sebacic acid,dodecanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, withsuccinic acid and adipic acid being preferred.

The diol ingredient is preferably ethylene glycol and/or aliphatic diolhaving the averaged number of carbon atoms of more than 2 and not morethan 3.0. the ratio of ethylene glycol in the diol ingredient ispreferably equal to or more than 50 mol %, or more preferably equal toor more than 75 mol %. The aliphatic diol includes alkyl diols andalicyclic diols, and examples thereof include ethylene glycol,1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol,2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol,2,2-dimethyl-1,3-propanediol (neopentyl glycol),2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane),2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane),3-methyl-1,5-pentanediol, 1,6-hexanediol,2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol,2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol,1,12-octadecanediol and diethylene glycol. One kind of or a mixture oftwo or more kinds of these aliphatic diols is preferably used togetherwith ethanediol.

Among these aliphatic diols, ethylene glycol, 1,2-propanediol and1,3-propanediol are preferred, and ethylene glycol and 1,2-propanediolare more preferred.

As the polycondensed ester-type plasticizer, the polycondensed esterhaving the terminal OH forming esters with a monocarboxylic acid arepreferable. Preferred examples of the monocarboxylic acid used forcapping include acetic acid, propionic acid and butenoic acid. Amongthese, acetic acid and propionic acid are more preferred, and aceticacid is most preferred. Preferred examples of the monoalcohols used forcapping include methanol, ethanol, propanol, isopropanol, butanol andisobutanol, with methanol being most preferred. When the carbon numberof monocarboxylic acids used for the terminal end of the polycondensedester is 3 or less, the loss on heating of the compound is not increasedand no surface failure is caused. And any mixture of two or more typesof monocarboxylic acids may be used for capping. The polycondensedesters having, at the both ends, the terminal OH forming ester withacetic acid or propionic acid are preferable; and the polycondensedesters having, at the both ends, the terminal OH forming ester withacetic acid are more preferable.

The number average molecular weight of the polycondensed ester ispreferably from 700 to 2,000, more preferably from 800 to 1,500, stillmore preferably from 900 to 1,200. The number average molecular weightof the polycondensed ester for use in the present invention can bemeasured and evaluated by gel permeation chromatography.

Specific examples of the polycondensed ester for use in the presentinvention are set forth in Table 1, but the present invention is notlimited thereto.

TABLE 2 Dicarboxylic acid Diol Ratio of Ratio of Averaged Number-Aromatic Aliphatic dicarboxylic Aliphatic numbers of carbon averageddicarboxylic dicarboxylic acid(s) Aliphatic diol(s) atoms in AliphaticBoth molecular acid acid (mol %) diol(s) (mol %) diol(s) (mol %)terminals weight P-1  PA AA 10/90 Ethylene glycol 100 2.0 acetyl ester1000 residue P-2  PA AA 25/75 Ethylene glycol 100 2.0 acetyl ester 1000residue P-3  PA AA 50/50 Ethylene glycol 100 2.0 acetyl ester 1000residue P-4  PA SA  5/95 Ethylene glycol 100 2.0 acetyl ester 1000residue P-5  PA SA 20/80 Ethylene glycol 100 2.0 acetyl ester 1000residue P-6  TPA AA 15/85 Ethylene glycol 100 2.0 acetyl ester 1000residue P-7  TPA AA 50/50 Ethylene glycol 100 2.0 acetyl ester 1000residue P-8  TPA SA  5/95 Ethylene glycol 100 2.0 acetyl ester 1000residue P-9  TPA SA 10/90 Ethylene glycol 100 2.0 acetyl ester 1000residue P-10 TPA SA 15/85 Ethylene glycol 100 2.0 acetyl ester 1000residue P-11 TPA SA 50/50 Ethylene glycol 100 2.0 acetyl ester 1000residue P-12 TPA SA 70/30 Ethylene glycol 100 2.0 acetyl ester 1000residue P-13 TPA/PA AA 10/10/80 Ethylene glycol 100 2.0 acetyl ester1000 residue P-14 TPA/PA AA 20/20/60 Ethylene glycol 100 2.0 acetylester 1000 residue P-15 TPA/PA AA/SA 10/10/40/40 Ethylene glycol 100 2.0acetyl ester 1000 residue P16 TPA AA/SA 10/30/60 Ethylene glycol 100 2.0acetyl ester 1000 residue P-17 TPA AA/SA 10/30/60 Ethylene glycol/ 50/502.5 acetyl ester 1000 1,2-propane residue diol P-18 TPA AA/SA 10/30/601,2-propane 100 3.0 acetyl ester 1000 diol residue P-19 TPA AA/SA10/30/60 Ethylene glycol 100 2.0 acetyl ester 700 residue P-20 TPA AA/SA10/30/60 Ethylene glycol 100 2.0 acetyl ester 850 residue P-21 TPA AA/SA10/30/60 Ethylene glycol 100 2.0 acetyl ester 1200 residue P-22 TPAAA/SA 10/30/60 Ethylene glycol 100 2.0 acetyl ester 1600 residue P-23TPA AA/SA 10/30/60 Ethylene glycol 100 2.0 acetyl ester 2000 residueP-24 TPA AA/SA 10/30/60 Ethylene glycol 100 2.0 propionyl ester 1000residue P-25 TPA AA/SA 10/30/60 Ethylene glycol 100 2.0 butanoyl ester1000 residue P-26 TPA AA/SA 10/30/60 Ethylene glycol 100 2.0 benzoylester 1000 residue P-27 TPA AA/SA 20/40/40 Ethylene glycol 100 2.0acetyl ester 1000 residue P-28 2,6-NPA AA/SA 20/40/40 Ethylene glycol100 2.0 acetyl ester 1200 residue P-29 1,5-NPA AA/SA 20/40/40 Ethyleneglycol 100 2.0 acetyl ester 1200 residue P-30 1,4-NPA AA/SA 20/40/40Ethylene glycol 100 2.0 acetyl ester 1200 residue P-31 1,8-NPA- AA/SA20/40/40 Ethylene glycol 100 2.0 acetyl ester 1200 residue P-32 2,8-NPAAA/SA 20/40/40 Ethylene glycol 100 2.0 acetyl ester 1200 residue InTable, PA means phthalic acid; TPA means terephthalic acid; IPA meansisophthalic acid; AA means adipic acid; SA means succinic acid; 2,6-NPAmeans 2,6-naphthalene dicarboxylic acid; 2,8-NPA means 2,8-naphthalenedicarboxylic acid; 1,5-NPA means 1,5-naphthalene dicarboxylic acid;1,4-NPA means 1,4-naphthalene dicarboxylic acid; and 1,8-NPA means1,8-naphthalene dicarboxylic acid.

As to the synthesis of the polycondensed ester for use in the presentinvention, the polycondensed ester can be easily synthesized in a usualmanner either by a heat-melting condensation method using apolyesterification or transesterification reaction of the dicarboxylicacid, the diol and, if desired, a monocarboxylic acid or monoalcohol forend capping or by an interfacial condensation reaction of acid chloridesof these acids with glycols. Details of these polyester-basedplasticizers are described in Koichi Murai (compiler), Kaso-zai SonoRiron to Oyo (Plasticizers, and Theory and Application Thereof) (SaiwaiShobo, 1st edition, published on Mar. 1, 1973). Furthermore, thematerials described, for example, in JP-A-05-155809, JP-A-05-155810,JP-A-05-197073, JP-A-2006-259494, JP-A-07-330670, JP-A-2006-342227 andJP-A-2007-003679 can also be used.

The amount added of the polycondensed ester plasticizer for use in thepresent invention is preferably from 0.1 to 70 mass %, more preferablyfrom 1 to 65 mass %, and most preferably from 3 to 60 mass %, based onthe amount of the cellulose acylate.

The content of the starting materials and the side products in thepolycondensation-ester plasticizer, concretely aliphatic diols,dicarboxylates, diol esters and others, that may be in the film ispreferably less than 1%, more preferably less than 0.5%. Thedicarboxylate includes dimethyl phthalate, di(hydroxyethyl) phthalate,dimethyl terephthalate, di(hydroxyethyl) terephthalate, di(hydroxyethyl)adipate, di(hydroxyethyl) succinate, etc. The diol ester includesethylene diacetate, propylene diacetate, etc.

As the plasticizer for the polymer film of the invention, also preferredis a methyl methacrylate (MA) oligomer plasticizer. The MA oligomerplasticizer may be combined with the above-mentioned saccharideplasticizer for use herein. In the mode of combination use, the ratio bymass of the MA oligomer plasticizer to the saccharide plasticizer ispreferably from 1/2 to 1/5, more preferably from 1/3 to 1/4. Examples ofthe MA-oligomer plasticizer include oligomers having a repeating unitshown below.

The weight-averaged molecular weight is preferably from about 500 toabout 2000, more preferably from about 700 to about 1500; and morepreferably from about 800 to about 1200.

Examples of the MA-oligomer plasticizer include both of oligomers of MAalone and oligomers having other repeating unit (s) along with therepresenting unit derived from MA. Examples of the other repeating unit(s) include any units derive from ethyl acrylate, i- or n-propylacrylate, n-, s- or t-butyl acrylate, n-, i- or s-pentyl acrylate, n- ori-hexyl acrylate, n- or i-heptyl acrylate, n- or i-octyl acrylate, n- ori-nonyl acrylate, n- or i-myristyl acrylate, 2-ethylhexyl acrylate,ε-caprolactam acrylate, 2-hydroxyethyl acylate, 2-hydroxypropylacrylate, 3-hydroxypropyl acrylate,4-hydroxybutyl acrylate,2-hydroxybutyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylateand methacrylates formed by replacing acrylic acid in the acrylates withmethacrylic acid. Monomers having an aromatic ring(s) such as styrene,methyl styrene and hydroxy styrene may be used. As the other monomer(s),acrylate monomer(s) or methacrylate monomer(s), having no aromatic ring,are preferable.

The MA-oligomer plasticizer, having two or more repeating units derivedfrom X which is a monomer having a hydrophilic group(s) and from Y whichis a monomer having no hydrophilic group, may be used. Among sucholigomers, those having a molar ratio of X to Y, X/Y, of from 1/1 to1/99 are preferable.

The MA-oligomer may be prepared in reference to the method described inJP-A No. 2003-12859.

(Polymer Plasticizer)

The polymer film of the invention may contain any other polymerplasticizer along with or in place of any one of the above-mentionedsaccharide plasticizer, polycondensate ester plasticizer and MA oligomerplasticizer. The other polymer plasticizer includespolyester-polyurethane plasticizers, aliphatic hydrocarbon polymers,alicyclic hydrocarbon polymers; vinylic polymers such as polyvinylisobutyl ether, poly-N-pyrrolidone, etc.; styrenic polymers such aspolystyrene, poly-4-hydroxystyrene, etc.; polyethers such aspolyethylene oxide, polypropylene oxide, etc.; polyamides,polyurethanes, polyureas, phenol-formaldehyde condensates,urea-formaldehyde condensates, polyvinyl acetate, etc.

(Compound Having at Least Two Aromatic Rings)

The polymer film of the invention may contain a compound having at least2 aromatic rings. The compound has an effect of controlling the opticalproperties of the cellulose ester film. For example, when the celluloseester film of the invention is sued as an optical compensation film, itis effectively stretched for controlling the optical properties,especially Re thereof to be on a desired level. For increasing Rethereof, the in-plane refractive anisotropy of the film may beincreased, for which one method comprises regulating the main chainorientation by stretching. As combined with stretching, a compoundhaving a large refractivity anisotropy may be added to the film forfurther increasing the refractive anisotropy of the film. For example,when the film to which a compound having at least 2 aromatic ring isadded as an additive thereto is stretched, the main chain of the polymerconstituting the film is oriented, and with that, the compound itselfbecomes well orientable and the film may be controlled to have desiredoptical properties with ease.

The compound having at least 2 aromatic rings includes, for example,triazine compounds as in JP-A 2003-344655, rod-shaped compounds as inJP-A 2002-363343, crystalline compounds as in JP-A 2005-134884 and2007-119737, etc. More preferred are triazine compounds and rod-shapedcompounds. Two or more different types of compounds having at least 2aromatic rings may be used, as combined. The molecular weight of thecompound having at least 2 aromatic rings is preferably from 300 to 1200or so, more preferably from 400 to 1000.

The mass percent of the compound having at least two aromatic rings tothe cellulose acylate resin is preferably 0.05% to 10%, more preferably0.5% to 8%, and most preferably 1% to 5%. The compound having twoaromatic rings may also function as the compound represented by Formula(1) or (2) that is used in the present invention. However, if a compoundhaving two aromatic rings has a 1,3,5-triazine ring structure but doesnot satisfy Formulae (1) and (2), the mass percent of the compoundhaving two aromatic rings to the cellulose acylate resin rangespreferably from 0.05% to 10%, more preferably from 0.5% to 8%, and mostpreferably from 1% to 5%, from the viewpoint of reducing the humiditydependency.

(Optical Anisotropy-Controlling Agent)

An optical anisotropy-controlling agent may be added to the polymerfilm. For example, its examples include “Rth-reducing compounds”described in JP-A 2006-30937, pp. 23-72.

(Mat Agent Fine Particles)

The polymer film of the invention may contain fine particles as a matagent. The fine particles usable in the invention are silicon dioxide,titanium dioxide, aluminium oxide, zirconium oxide, calcium carbonate,talc, clay, calcined kaolin, calcined calcium silicate, calcium silicatehydrate, aluminium silicate, magnesium silicate, and calcium phosphate.Preferably, the fine particles contain silicon as they are effective forreducing the haze of films. Especially preferably, they are silicondioxide.

The silicon dioxide microparticles may be commercially availableproducts such as Aerosils R972, R972V, R974, R812, 200, 200V, 300, R202,OX50, and TT600 (manufactured by Nippon Aerosil Co., Ltd.). Zirconiumoxide microparticles that can be used are, for example, commerciallyavailable Aerosils R976 and R811 (manufactured by Nippon Aerosil Co.,Ltd.).

A polymer film containing particles having a small average secondaryparticle diameter can be produced with a dispersion of microparticles.In a cellulose acylate film as an example, several processes are knownfor preparing a dispersion of microparticles. For example, amicroparticle dispersion can be prepared by mixing a solvent andmicroparticles with stirring to prepare a microparticle dispersion inadvance, adding this microparticle dispersion to a small amount ofseparately prepared cellulose acylate solution and stirring the mixtureto prepare a solution, and further mixing the solution with a celluloseacylate dope solution as a main component. This process is preferable inthat the dispersibility of silicon dioxide microparticles is high andthat the silicon dioxide microparticles hardly re-aggregate.Alternatively, a microparticle dispersion can be prepared by adding asmall amount of cellulose acylate to a solvent and stirring the mixtureto prepare a solution, adding microparticles to the solution anddispersing the mixture with a disperser to prepare amicroparticle-containing solution, and sufficiently mixing themicroparticle-containing solution with a dope solution with an in-linemixer. Any of these processes can be employed, and any other process maybe employed without limitation.

The solvent used in the preparation process described above can be loweralcohol. Preferred examples of the lower alcohol include methanol,ethanol, propanol, isopropanol, and butanol. Any other solvent can beused as well as lower alcohol, and preferred examples of the solvent arethose used information of a film from cellulose acylate.

(Low-Molecular Plasticizer, Degradation Inhibitor, Release Agent)

Various additives (e.g., low-molecular plasticizer, UV inhibitor,degradation inhibitor, release agent, IR absorbent, etc.) may be addedto the polymer film in the process of producing the film, depending onthe applications of the film. The additives may be solid or oily, orthat is, they are not specifically defined in point of their meltingpoint and boiling point thereof. For example, for the additive, UVabsorbents at 20 degrees Celsius or lower and at 20 degrees Celsius orhigher may be mixed, or plasticizers may also be mixed in the samemanner. For example, these are described in JP-A 201-151901. IRabsorbent dyes are described in, for example, JP-A 2001-194522. The timeat which the additive is added may be in any stage in the step of dopepreparation; however, the additive may be added in the final stage ofthe dope preparation step. Not specifically defined, the amount of thematerial to be added may be any one capable expressing the functionthereof. In case where the cellulose ester film is formed of plurallayers, then the type and the amount of the additive to be added to theconstitutive layers may differ. For example, as in JP-A 2001-151902, therelated technique is known in the art. Regarding the details of theadditives, the materials described in Hatsumei Kyokai DisclosureBulletin No. 2001-1745 (published in Mar. 15, 2001 by Hatsumei Kyokai)in p.p. 16-22 are preferred for use in the invention.

(1-5) Production Method for Polymer Film:

The polymer film of the invention is preferably produced according to asolvent-casting method. According to a solvent-casting method, a dopeprepared by dissolving a polymer in an organic solvent is cast onto thesurface of a support of a metal or the like, and dried thereon to form afilm. Next, the film is peeled away from the support surface, andstretched.

The cellulose acylate film is preferably produced according to asolvent-casting method. Examples of production of cellulose ester filmaccording to a solvent-casting method are given in U.S. Pat. Nos.2,336,310, 2,367,603, 2,492,078, 2,492,977, 2,492,978, 2,607,704,2,739,069 and 2,739,070, British Patents 640731, 736892, JP-B 45-4554,49-5614, and JPA Nos. syo 60-176834, syo 60-203430, and syo 62-115035,and their descriptions are referred to herein. The cellulose acylatefilm may be stretched. Regarding the method and condition for stretchingtreatment, for example, referred to are JPA Nos. syo 62-115035, hei4-152125, hei 4-284511, hei 4-298310, and hei 11-48271.

(1-6) Characteristics of Polymer Film: (Re and Rth)

The preferred range of the optical characteristics of the polymer filmof the invention changes depending on the use of the film. In anembodiment where the film is used in a VA-mode liquid-crystal displaydevice, preferably, its Re(589) is from 30 nm to 200 nm, and itsRth(589) is from 70 nm to 400 mm; more preferably, its Re(589) is from30 nm to 150 nm, and its Rth(589) is from 100 nm to 300 nm; even morepreferably, its Re(589) is from 40 nm to 100 nm, and its Rth(589) isfrom 100 nm to 250 nm.

The Re and Rth of a film are measured after leaving the film under anenvironment of a temperature of 25° C. and a relative humidity of 60%for a sufficient time (more than 2 hours, e.g., 12 hours or 24 hours) atthe same temperature and the same relative humidity, unless otherwisespecified.

(Humidity Dependency of Re and Rth)

The polymer film of the present invention is characterized by a smallfluctuation in Re and/or Rth depending on humidity, specifically, asmall fluctuation between the Re (also referred to as Re [25° C.,RH10%]) of a film humidified at a relative humidity of 10% at 25° C. for2 hours and the Re (also referred to as Re [25° C., RH80%]) of the filmhumidified at a relative humidity of 80% at 25° C. for 2 hours and/or asmall fluctuation between the Rth (also referred to as Rth [25° C.,RH10%]) of the film humidified at a relative humidity of 10% at 25° C.for 2 hours and the Rth (also referred to as Rth [25° C., RH80%]) of thefilm humidified at a relative humidity of 80% at 25° C. for 2 hours. Thefilm of the present invention has reduced humidity dependency of opticalcharacteristics to suppress the fluctuations in Re and Rth even under ahumidity-varying environment and thereby can have retardation in apreferred range.

In the polymer film of the present invention, the humidity dependency ofRe (ΔRe=|Re [25° C., RH10%]−Re [25° C., RH80%]|) is preferably 10 nm orless, more preferably 9 nm or less, and most preferably 8 nm or less.

In the polymer film of the present invention, the humidity dependency ofRth (ΔRth=|Rth [25° C., RH10%]−Rth [25° C., RH80%]|) is preferably 21 nmor less, more preferably 20 nm or less, and most preferably 19 nm orless.

(Film Thickness)

In an embodiment where the polymer film of the invention is used as apart in a device that is desired to have a thinned body, for example, asa part of a liquid-crystal display device or the like, the film ispreferably thinner. However, if too thin, the film could not exhibit theoptical characteristics necessary for the use. In an embodiment wherethe film of the invention is used as an optical compensatory film in aliquid-crystal display device, or as a protective film for a polarizer,the film thickness is preferably from 20 to 80 μm or so, more preferablyfrom 25 to 70 μm or so, even more preferably from 30 to 60 μm or so.

3. Application of Polymer Film

The polymer film of the present invention can be used in variousapplications. For example, the polymer film can be used as a retardationfilm (hereinafter, also referred to as an optical compensation film) ofa liquid crystal display or as a protective film of a polarizing plate.

(Retardation Film)

The polymer film of the present invention can be used as a retardationfilm. “A retardation film or an optical compensation film” is usuallyused in a display such as a liquid crystal display and is an opticalmaterial having optical anisotropy and is synonymous with, for example,an optically compensatory sheet. In a liquid crystal display, theoptical compensation film is used for improving the contrast of thedisplay screen or improving the viewing angle characteristics or thetint.

In order to obtain desired Re and Rth levels, a plurality of the polymerfilms of the present invention may be laminated, or the polymer film ofthe present invention may be laminated another film. The films can belaminated with an adhesive or a bonding agent.

(Polarizing Plate)

The polymer film of the invention may be used as a protective film forpolarizing plate, and the invention provides a polarizing platecomprising the film. One example of the polarizing plate of theinvention comprises a polarizing film and two protective films(transparent films) for protecting both surfaces of the polarizing film,in which the cellulose ester film of the invention is used as at leastone of the polarizer-protective films. In an embodiment where thecellulose ester film of the invention is used as a support and anoptically-anisotropic layer of a liquid-crystal composition is formed onthe surface of the support, and where the cellulose ester film is usedas a protective film for a polarizing plate, it is desirable that theback side (on which the optically-anisotropic layer is not formed) ofthe polymer film of the invention serving as a support is stuck to thesurface of the polarizing film.

In case where the polymer film of the invention is used as a protectivefilm for the polarizing plate, the polymer film of the invention ispreferably hydrophilicated through the above-mentioned surface-treatment(e.g., as described in JP-A 6-94915 and 6-118232), and for example, thefilm is preferably processed for glow discharge treatment, coronadischarge treatment, or alkali saponification. In particular, thesurface treatment of the film is most preferably alkali saponification.

As the polarizing film, for example, usable is a film produced bydipping a polyvinyl alcohol film in an iodine solution and stretchingit. In case where the polarizing film produced by dipping a polyvinylalcohol film in an iodine solution and stretching it is used, thesurface-treated surface of the transparent cellulose ester film of theinvention may be directly stuck to both surfaces of the polarizing filmwith an adhesive. In the production method of the invention, it isdesirable that the polymer film is directly stuck to the polarizing filmin the manner as above. As the adhesive, usable is an aqueous solutionof polyvinyl alcohol or polyvinyl acetal (e.g., polyvinyl butyral) or alatex of a vinylic polymer (e.g., polybutyl acrylate). Especiallypreferred as the adhesive is an aqueous solution of acompletely-saponified polyvinyl alcohol.

In general, in a liquid-crystal display device, a liquid-crystal cell isdisposed between two polarizing plates. Therefore, the device has fourpolarizer-protective films. The polymer film of the invention may beused as any of those four polarizer-protective films, but the polymerfilm of the invention is especially useful as the protective film to bedisposed between the polarizing film and the liquid-crystal layer(liquid-crystal cell) in the liquid-crystal display device. As theprotective film to be disposed on the side of the polarizing filmopposite to the side of the polymer film of the invention, a transparenthard coat layer, an antiglare layer, an antireflection layer or the likemay be disposed, and in particular, the film of the invention isfavorable as the polarizer-protective film to be disposed as theoutermost surface layer on the display panel side of the liquid-crystaldisplay device.

(Liquid-Crystal Display Device)

The polymer film of the invention and the optically-compensatory filmand the polarizing plate comprising the film can be used in variousdisplay modes of liquid-crystal display devices. Various liquid-crystalmodes where the film of the invention can be used are described. Aboveall, the polymer film of the invention and the optically-compensatoryfilm and the polarizing plate comprising the film are favorably used inVA-mode liquid-crystal display devices. The liquid-crystal displaydevices may be any of transmission-mode, reflection-mode orsemitransmission-mode devices.

FIG. 1 shows a schematic cross-sectional view of one example of aliquid-crystal display device of the invention. In FIG. 1, the upperside is a viewers' side (panel side), and the lower side is a backlightside.

The VA-mode liquid-crystal display device of in FIG. 1 comprises aliquid-crystal cell LC (comprising an upper substrate 1, a lowersubstrate 3 and a liquid-crystal layer 5), and a pair of an upperpolarizing plate P1 and a lower polarizing plate P2 disposed to sandwichthe liquid-crystal cell LC therebetween. In general, polarizing filmsare incorporated into the liquid-crystal display device as polarizingplates having a protective film on both surfaces thereof; however, inFIG. 1, the outer protective film of the polarizing film is omitted. Thepolarizing plates P1 and P2 each have a polarizing film 8 a and 8 b,respectively; and they are so disposed that the absorption axes 9 a and9 b thereof are perpendicular to each other. The liquid-crystal cell LCis a VA-mode liquid-crystal cell, and at the time of black level ofdisplay, the liquid-crystal layer 5 is in homeotropic alignment as inFIG. 1. The upper substrate 1 and the lower substrate 3 each have analignment film (not shown) and an electrode layer (not shown) on theinner surface thereof; and the substrate 1 has a color filter layer (notshown) on the viewers' side inner surface thereof.

Between the upper substrate 1 and the upper polarizing film 8 a, andbetween the lower substrate 3 and the lower polarizing film 8 b,disposed are retardation films 10 a and 10 b, respectively. Theretardation films 10 a and 10 b are polymer films of the invention. Theretardation films 10 a and 10 b are so disposed that the in-plane slowaxes 11 a and 11 b thereof could be perpendicular to the absorption axes9 a and 9 b of the upper polarizing film 8 a and the lower polarizingfilm 8 b, respectively. Specifically, the retardation films 10 a and 10b are so disposed that their slow axes are perpendicular to each other.The retardations films 10 a and 10 b each comprising the polymer film ofthe invention contribute toward reducing the light leakage and the colorshift that may occur in oblique directions at the time of black level ofdisplay.

(Hard Coat Film, Antiglare Film, Antireflection Film)

The polymer film of the invention may be applied to a hard coat film, anantiglare film, or an antireflection film, as the case may be. For thepurpose of enhancing the visibility of flat panel displays such as LCD,PDP, CRT, EL and the like, any or all of a hard coat layer, an antiglarelayer and an antireflection layer may be given to one or both surfacesof the transparent polymer film of the invention. Preferred embodimentsof such antiglare film and antireflection film are described in detailin Hatsumei Kyokai Disclosure Bulletin (No. 2001-1745, published on Mar.15, 2001 by Hatsumei Kyokai), pp. 54-57, and are favorably applicable tothe cellulose ester film of the invention.

EXAMPLES

The characteristic features of the invention are described moreconcretely with reference to the following Examples and ComparativeExamples. In these Examples, the material used, its amount and theratio, the details of the treatment and the treatment process may besuitably modified or changed not overstepping the sprit and the scope ofthe invention. Accordingly, the invention should not be limitativelyinterpreted by the Examples mentioned below.

Example 1a Synthetic Example of Compound in Compound Group A Representedby Formula (1) Synthetic Example 1a-1 Synthesis-1 of Compound (1-2)

2,4-Diamino-6-methylpyrimidine was synthesized in accordance with theprocess described in Aust. J. Chem., 1984, vol. 37, pp. 1195-1201.

Guanidine hydrochloride (23.8 g) was added to methanol (50 mL) and asolution of sodium methoxide in 28% methanol (51 mL), followed bystirring at room temperature for 30 minutes. Subsequently, theprecipitated salt was removed by filtration, followed by concentrationunder reduced pressure to give a guanidine-free product solution. Then,3-amino crotononitrile (16.4 g) and 1-butanol (60 mL) were added to thesolution. The reaction solution was stirred with heating at 110° C. for10 hours under a nitrogen gas flow. After completion of the reaction,the precipitated salt was removed by hot filtration, and 100 mL ofacetone was added to the remaining solution, followed by stirring underice cooling for 30 minutes to give a crude product. The crude productwas recrystallized from acetone to yield 10.5 g of2,4-diamino-6-methylpyrimidine.

Methyl benzoate (23 g: 169 mmol) and sodium methoxide (22 g: 407 mmol)were added to a solution of 2,4-diamino-6-methylpyrimidine (10 g: 81mmol) in N-ethylpyrrolidone (100 mL), followed by stirring with heatingat 40° C. for 2 hours. The temperature of the reaction system wasdecreased to room temperature. The reaction solution was poured into a1N aqueous hydrochloric acid solution, and the solid component wascollected by filtration. The crude product was recrystallized from2-propanol to yield compound (1-2).

The NMR spectrum of produced compound (1-2) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) δ (ppm) 2.50 (3H,s) 7.45-7.70 (6H, m) 7.90 (1H, s) 7.95-8.05 (4H, m) 10.88 (1H, s) 11.10(1H, s)

Synthetic Example 1a-2 Synthesis-2 of Compound (1-2)

2,4-Diamino-6-methylpyrimidine (2 g: 16 mmol) and phenyl benzoate weremixed in xylene, followed by reflux heating for 6 hours. HPLC confirmedthat the yield of compound (1-2) was 60%.

Synthetic Example 2a Synthesis of Compound (1-8)

The compound was synthesized as in Synthetic example 1a-1 except that2,4-diamino-6-hydroxypyrimidine was used as a starting material in placeof 2,4-diamino-6-methylpyrimidine in Synthetic example 1a-1. Thereaction solution was poured into an aqueous acetic acid solution,followed by adjusting the solution to pH 6. The precipitated solid wascollected by filtration and was washed with acetonitrile and methanolwith heating to yield compound (1-8).

The NMR spectrum of produced compound (1-8) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) δ (ppm) 6.88 (1H,s) 7.48-7.68 (4H, m) 7.92 (2H, d) 8.01 (2H, d) 10.36 (1H, s) 11.64 (1H,s) 12.11 (1H, s)

Synthetic Example 3a-1 Synthesis-1 of Compound (1-9)

The compound was synthesized as in Synthetic example 1a-1 except that 2,4-diamino-6-methoxypyrimidine was used as a starting material in placeof 2,4-diamino-6-methylpyrimidine in Synthetic example 1a-1 and that thefollowing processes were performed.

2,4-Diamino-6-methoxypyrimidine was synthesized in accordance with themethod described in J. Bioorg. Med. Chem., 1998, vol. 6, pp. 1057-1067and was used without purification for the subsequent step.

2,4-Diamino-6-chloropyrimidine (21.9 g: 150 mmol) was added to methanol(20 mL) and toluene (80 mL) under a nitrogen gas flow, and a solution ofsodium methoxide in 28% methanol (153 mL) was dropwise added thereto atroom temperature. Subsequently, the mixture was refluxed in a hot waterbath at 80° C. while the solvent was being distilled off by a Dean-Starktrap. During the reflux, toluene (60 mL) was added to the reactionsolution, followed by refluxing. The reaction system was cooled to 50°C., and a mixture of N-ethylpyrrolidone (60 mL) and methyl benzoate (53g: 485 mol) was added thereto, followed by stirring with heating at 45°C. for 3 hours. The temperature of the reaction system was decreased toroom temperature, and then the reaction solution was added to a liquidmixture of toluene (200 mL), water (200 mL), and acetic acid (43 mL).The organic layer was separated, and 150 mL of 1N aqueous acetic acidsolution was added thereto under heating for separation. This separationstep was repeated twice, and water (200 mL) was added to the organiclayer, followed by cooling to room temperature to precipitate theproduct. The crude product was recrystallized from acetonitrile to yield30 g (yield: 57%) of compound (1-9).

The NMR spectrum of produced compound (1-9) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) δ (ppm) 3.90 (3H,s) 7.39 (1H, s) 7.45-7.70 (6H, m) 7.90-8.05 (4H, m) 10.78 (1H, s) 11.00(1H, s)

Synthetic Example 3a-2 Synthesis-2 of Compound (1-9)

2,4-Diamino-6-chloropyrimidine (17.34 g: 120 mmol) and sodium methoxide(38.9 g) were sequentially added to t-butanol (60 mL) andN-ethylpyrrolidone (30 mL) under a nitrogen gas flow, followed bystirring with heating at 80° C. for 2 hours. The reaction solution wascooled to 60° C., and methyl benzoate (38.9 g: 288 mol) was dropwiseadded thereto, followed by stirring with heating at 60° C. for 2 hours.The reaction solution was added to a liquid mixture of iced water (130mL) and concentrated hydrochloric acid (51 mL), followed by heating to50° C. to completely dissolve the solid component. The organic layer wasseparated, and methanol (100 mL) and water (100 mL) were added thereto,followed by stirring under ice cooling for 1 hour. The precipitatedproduct was collected by filtration, and the resulting crystals werewashed with a poured methanol/water solvent mixture and then water.After ventilation drying at 50° C. for 13 hours, 38 g (yield: 85%) ofcompound (1-9) was yielded.

Synthetic Example 3a-3 Synthesis-3 of Compound (1-9)

The crystals (5 g) prepared in Synthetic example 3a-1 were dispersed inacetonitrile/water (30 mL/20 mL), followed by stirring at roomtemperature for 2 hours. The precipitated solid was collected byfiltration to yield compound (1-9) having a different water contentratio.

Synthetic Example 3a-4 Synthesis-4 of Compound (1-9)

The crystals prepared in Synthetic example 3a-2 in a molten state weredried at 150° C. under reduced pressure for 3 hours, followed byquenching to yield amorphous compound (1-9). The water content ratio ofthe resulting compound immediately after the drying was less than 0.5%.

Synthetic Example 3a-5 Synthesis-5 of Compound (1-9)

The crystals (3.5 g) prepared in Synthetic example 3a-1 were dissolvedin ethyl acetate (20 mL), and concentrated hydrochloric acid (1 mL) wasadded thereto, followed by stirring at room temperature for 1 hour. Theprecipitated hydrochloride was collected by filtration.

The NMR spectrum of produced compound (1-9) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) δ (ppm) 3.96 (3H,s) 6.8 (1H, br) 7.39 (1H, s) 7.50-7.68 (6H, m) 7.99 (2H, m) 8.08 (2H, m)11.4 (1H, br) 11.6 (1H, br)

Synthetic Example 3a-6 Synthesis-6 of Compound (1-9)

The crystals prepared in Synthetic example 3a-1 were recrystallized fromvarious solvents to yield crystals having different water content ratioand different solvent content ratio as shown in the following table.

TABLE 3 Example Water Solvent of Recrystallization content contentCollection recrystallization solvent ratio ratio rate 1 Methanol 5.0%Contain 57% methanol 2 Heptane/ 3.1% Contain 87% isopropanol isopropanol(2/1) 3 t-Butanol 0.4% Contain 100%  t-butanol

Synthetic Example 4a Synthesis of Compound (2-1)

The compound was synthesized as in Synthetic example 1a-1 except that2,4-diaminopyrimidine and methyl m-methylbenzoate were used as startingmaterials in place of 2,4-diamino-6-methylpyrimidine and methylbenzoate, respectively, in Synthetic example 1a-1.

The NMR spectrum of produced compound (2-1) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) δ (ppm) 2.38 (6H,s) 7.35-7.50 (4H, m) 7.74-7.90 (4H, m) 7.98 (1H, s) 8.67 (1H, s) 10.84(1H, s) 11.10 (1H, s)

Synthetic Example 5a Synthesis of Compound (2-2)

The compound was synthesized as in Synthetic example 1a-1 except thatmethyl m-methylbenzoate was used in place of methyl benzoate inSynthetic example 1a-1 and that the following processes were performed.

Methyl m-methylbenzoate (72.5 g: 485 mmol) and sodium methoxide (35 g:650 mmol) were added to a solution of 2,4-diamino-6-methylpyrimidine (20g: 161 mmol) in N-ethylpyrrolidone (140 mL), followed by stirring withheating at 40° C. for 3 hours. The temperature of the reaction systemwas decreased to room temperature, and the reaction solution was addedto a liquid mixture of water (190 mL), concentrated hydrochloric acid(72.5 mL), and ethyl acetate (50 mL), under ice cooling. The resultingsolid (hydrochloride of compound (2-2)) was collected by filtration. Thehydrochloride was added to saturated aqueous sodium bicarbonate solution(160 mL) and ethyl acetate (150 mL), followed by stirring with heatingfor dissolution. The resulting solution was cooled to room temperatureto precipitate the product. The crude product was collected byfiltration and was recrystallized from acetonitrile to yield 47 g(yield: 81%) of compound (2-2). The NMR spectrum of produced compound(2-2) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) δ (ppm) 2.38 (6H,s) 2.50 (3H, s) 7.36-7.47 (4H, m) 7.70-7.90 (5H, m) 10.77 (1H, s) 10.99(1H, s)

Synthetic Example 5a-2 Synthesis-2 of Compound (2-2)

2,4-Diamino-6-methylpyrimidine (2.4 g: 20 mmol), triethylamine (6.97mL), and THF (20 mL) were mixed, and m-methylbenzoyl chloride (7.7 g: 50mmol) was dropwise added thereto at room temperature, followed bystirring with heating at 40° C. for 6 hours. After cooling, the productwas extracted with ethyl acetate and was recrystallized from ethylacetate/hexane to yield 2.1 g of compound (2-2).

Synthetic Example 6a Synthesis of Compound (2-4)

The compound was synthesized as in Synthetic example 1a-1 except that2,4-diamino-6-methylaminopyrimidine and methyl m-methylbenzoate wereused as starting materials in place of 2,4-diamino-6-methylpyrimidineand methyl benzoate, respectively, in Synthetic example 1a-1.

The NMR spectrum of produced compound (2-4) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) δ (ppm) 2.35 (6H,s) 2.81 (3H, s) 7.15 (1H, s) 7.30-7.43 (5H, m) 7.65-7.85 (4H, m) 10.22(1H, s) 10.38 (1H, s)

Synthetic Example 7a Synthesis of Compound (2-8)

The compound was synthesized as in Synthetic example 1a-1 except that2,4-diamino-6-hydroxypyrimidine and methyl m-methylbenzoate were used asstarting materials in place of 2,4-diamino-6-methylpyrimidine and methylbenzoate, respectively, in Synthetic example 1a-1.

The NMR spectrum of produced compound (2-8) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) δ (ppm) 2.41 (6H,s) 6.89 (1H, s) 7.36-7.53 (4H, m) 7.70-7.88 (4H, m) 10.23 (1H, s) 11.54(1H, s) 11.99 (1H, s)

Synthetic Example 8a Synthesis of Compound (2-9)

The compound was synthesized as in Synthetic example 1a-1 except that2,4-diamino-6-methoxypyrimidine and methyl m-methylbenzoate were used asstarting materials in place of 2,4-diamino-6-methylpyrimidine and methylbenzoate, respectively, in Synthetic example 1a-1. The crude product waspurified by silica gel column chromatography using ethylacetate/n-hexane and recrystallized from ethyl acetate/n-hexane to yieldcompound (2-9).

The NMR spectrum of produced compound (2-9) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) δ (ppm) 2.40 (6H,s) 3.92 (3H, s) 7.35-7.45 (5H, m) 7.73-7.87 (4H, m) 10.67 (1H, s) 10.88(1H, s)

Synthetic Example 8a-2 Synthesis-2 of Compound (2-9)

2,4-Diamino-6-methoxypyrimidine (2.2 g: 20 mmol) was mixed withm-methylbenzoyl chloride (4.56 g: 50 mmol) and sodium bicarbonate (4.2g) in acetonitrile, followed by reflux heating for 6 hours. Aftercooling, the precipitated solid was collected by filtration, washed bydispersion in water, collected by filtration again, and washed withpoured water and acetonitrile to yield 2.1 g of compound (2-9).

Synthetic Example 9a Synthesis of compound (5-1), (5-2), (5-7), and(5-8)

Compounds (5-1), (5-2), (5-7), and (5-8) were prepared as in Syntheticexample 1a-1 except that methyl p-methylbenzoate, methylo-methylbenzoate, methyl m-methoxybenzoate, and methyl p-methoxybenzoatewere respectively used as starting materials in place of methyl benzoateand that the reaction was performed using sodium methoxide. Purificationwas performed by silica gel column chromatography and recrystallization.

Synthetic Example 10a Synthesis of Compound (6-13)

2-Amino-4-anilino-6-methoxypyrimidine was synthesized using2-amino-4,6-dichloropyrimidine as a starting material through2-amino-4-chloro-6-methoxypyrimidine. A solution of sodium methoxide in28% methanol (43 mL) at an internal temperature of 20° C. or less wasdropwise added to a mixture of 2-amino-4,6-dichloropyrimidine (32.8 g)and acetone (700 mL) under ice cooling. The reaction was furthercontinued at an internal temperature of 40° C. for 4 hours, and thesolution was concentrated under reduced pressure, followed by additionof 500 mL of water. The precipitated solid was collected by filtrationand was used without purification for the subsequent step. The crudeproduct of 2-amino-4-chloro-6-methoxypyrimidine, aniline (26.7 mL),methoxyethanol (150 mL), and hydrochloric acid (0.2 mL) were mixed,followed by stirring with heating at 120° C. for 3 hours. After cooling,the reaction solution was added to aqueous sodium bicarbonate (500mL)/ethyl acetate under ice cooling to extract the product with ethylacetate. After the concentration, purification by column chromatography(ethyl acetate/n-hexane) was performed to yield 14 g of2-amino-4-anilino-6-methoxypyrimidine.

2-Amino-4-anilino-6-methoxypyrimidine was synthesized as in Syntheticexample 1a-1 with methyl m-methylbenzoate and sodium methoxide. Thecrude product was purified by silica gel column chromatography usingmethylene chloride/methanol and was recrystallized from methylenechloride/n-hexane to yield compound (6-13).

The NMR spectrum of produced compound (6-13) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) δ (ppm) 2.39 (3H,s) 3.85 (3H, s) 5.87 (1H, s) 6.95 (1H, s) 7.23-7.30 (2H, m) 7.38-7.41(2H, m) 7.72-7.85 (4H, m) 9.40 (1H, s) 9.46 (1H, s)

Synthetic Example 11a Synthesis of Compound (6-14)

2-Amino-4-anilino-6-methylaminopyrimidine was synthesized, via2-amino-4-chloro-6-methylaminopyrimidine, with2-amino-4,6-dichloropyrimidine as a starting material.2-Amino-4,6-dichloropyrimidine (32.8 g), a 40% aqueous methylaminesolution (34.5 mL), and ethanol (300 mL) were mixed, followed bystirring at an internal temperature of 70° C. for 4 hours. Subsequently,the solvent was concentrated under reduced pressure, and crystallizationfrom acetonitrile was performed. The product was collected by filtrationand was used without purification for the subsequent step. The crudeproduct of 2-amino-4-chloro-6-methylaminopyrimidine, aniline (27.4 mL),methoxyethanol (100 mL), and hydrochloric acid (0.2 mL) were mixed,followed by stirring with heating at 120° C. for 3 hours. After cooling,the reaction solution was added to sodium bicarbonate water (500mL)/ethyl acetate under ice cooling to extract the product with ethylacetate. After concentration, purification by column chromatography(ethyl acetate/methanol) was performed to yield 18 g of2-amino-4-anilino-6-methylaminopyrimidine. Synthesis was performed as inSynthetic example 1a-1 with 2-amino-4-anilino-6-methylaminopyrimidine,methyl m-methylbenzoate, and sodium methoxide. The product was purifiedby silica gel column chromatography using ethyl acetate/n-hexane andrecrystallization from ethyl acetate/n-hexane to yield compound (6-14).

The NMR spectrum of produced compound (6-14) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) δ (ppm) 2.37 (3H,s) 2.75 (3H, d) 5.51 (1H, s) 6.87-6.91 (1H, m) 7.15-7.24 (2H, m)7.34-7.38 (2H, m) 7.65-7.74 (4H, m) 8.95 (1H, s) 10.02 (1H, s)

Synthetic Example 12a Synthesis of Compound (6-15)

The compound was synthesized as in Synthetic example 1a-1 except that2,4-diamino-6-hydroxypyrimidine and methyl p-tert-butylbenzoate wereused as starting materials in place of 2,4-diamino-6-methylpyrimidineand methyl benzoate, respectively, in Synthetic example 1a-1.

The NMR spectrum of produced compound (6-15) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) δ (ppm) 1.34(18H, s) 7.87 (1H, s) 7.51-7.63 (4H, m) 7.85-7.95 (4H, m) 10.21 (1H, s)11.57 (1H, s) 12.07 (1H, s)

Synthetic Example 13a Synthesis of Compound (6-16)

The compound was synthesized as in Synthetic example 5a except that2,4-diamino-6-chloropyrimidine and methyl benzoate were used as startingmaterials in place of 2,4-diamino-6-methylpyrimidine and methylm-methylbenzoate, respectively, in Synthetic example 5a. The productextracted from aqueous sodium bicarbonate solution/ethyl acetate wascollected by filtration, and no purification was performed.

The NMR spectrum of produced compound (6-16) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) δ (ppm) 1.34(18H, s) 7.87 (1H, s) 7.51-7.63 (4H, m) 7.85-7.95 (4H, m) 10.21 (1H, s)11.57 (1H, s) 12.07 (1H, s)

Synthetic Example 14a Synthesis of Compound (7-1)

The compound was synthesized as in Synthetic example 1a-1 except that2,6-diaminopyridine was used as a starting material in place of2,4-diamino-6-methylpyrimidine in Synthetic example 1a-1.

The NMR spectrum of produced compound (7-1) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) δ (ppm) 7.45-7.66(6H, m) 7.87-7.94 (3H, m) 7.95-8.10 (4H, m) 10.51 (2H, s)

Synthetic Example 15a Synthesis of Compound (7-2)

The compound was synthesized as in Synthetic example 1a-1 except that2,6-diaminopyridine and methyl m-methylbenzoate were used as startingmaterials in place of 2,4-diamino-6-methylpyrimidine and methylbenzoate, respectively, in Synthetic example 1a-1.

The NMR spectrum of produced compound (7-2) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) δ (ppm) 2.40 (6H,s) 7.37-7.45 (4H, m) 7.75-7.88 (7H, m) 10.40 (2H, s)

Synthetic Example 16a Synthesis of Compound (8-1)

Dicyandiamide (18 g: 214 mmol) and nickel (II) acetate (52 g: 209 mmol)were added to a solution of N-(2,5-dimethoxyphenyl)-3-oxobutanamide (50g: 211 mmol) in N-methylpyrrolidone (150 mL), followed by stirring withheating at 130° C. for 5 hours. The reaction solution was cooled to roomtemperature and was poured into saturated aqueous sodium bicarbonate,followed by extraction with ethyl acetate. The organic layer was driedover anhydrous sodium sulfate, and the solvent was distilled off with arotary evaporator. The crude product was washed with 2-propanol to yieldcompound (8-1).

The NMR spectrum of produced compound (8-1) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) δ (ppm) 2.28 (3H,s) 2.71 (3H, s) 2.77 (3H, s) 6.22 (2H, s) 6.40 (2H, s) 6.67 (1H, d) 6.97(1H, d) 7.59 (1H, s) 9.01 (1H, s)

Synthetic Example 17a Synthesis of Compound (8-2)

Methyl m-methylbenzoate (17 g: 113 mmol) and sodium methoxide (11 g: 204mmol) were added to a solution of 2-aminopyrimidine (10 g: 105 mmol) inN-ethylpyrrolidone (100 mL), followed by stirring with heating at 40° C.for 2 hours. The temperature of the reaction system was decreased toroom temperature. The reaction solution was poured into a 1N aqueoushydrochloric acid solution, and the solid component was collected byfiltration. The crude product was purified by silica gel columnchromatography (eluent was methanol: dichloromethane=1:10) to yieldcompound (8-2).

The NMR spectrum of produced compound (8-2) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) δ (ppm) 2.40 (3H,s) 7.25 (1H, t) 7.35-7.44 (2H, m) 7.72-7.84 (2H, m) 8.74 (2H, d) 10.91(1H, s)

Synthetic Example 18a Synthesis of Compound (8-3)

The compound was synthesized as in Synthetic example 17a except that2-amino-4,6-dimethylpyrimidine was used as a starting material in placeof 2-aminopyrimidine in Synthetic example 17a.

The NMR spectrum of produced compound (8-3) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) δ (ppm) 2.35-2.45(9H, m) 7.00 (1H, s) 7.35-7.40 (2H, m) 7.73-7.83 (2H, m) 10.72 (1H, s)

Synthetic Example 19a Synthesis of Compound (8-4)

The compound was synthesized as in Synthetic example 17a except that2-amino-4,6-dimethoxypyrimidine was used as a starting material in placeof 2-aminopyrimidine in Synthetic example 17a.

The NMR spectrum of produced compound (8-4) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) δ (ppm) 2.38 (3H,s) 3.88 (6H, s) 5.98 (1H, s) 7.35-7.42 (2H, m) 7.67-7.78 (2H, m) 10.69(1H, s)

Synthetic Example 20a Synthesis of Compound (8-5)

Dimethyl isophthalate (7.2 g: 37 mmol) and sodium methoxide (10 g: 185mmol) were added to a solution of 2-amino-4,6-dimethylpyrimidine (10 g:81 mmol) in N-ethylpyrrolidone (75 mL), followed by stirring withheating at 40° C. for 2 hours. The temperature of the reaction systemwas decreased to room temperature. The reaction solution was poured intoa 1N aqueous hydrochloric acid solution, and the solid component wascollected by filtration. The crude product was recrystallized fromacetonitrile to yield compound (8-5).

The NMR spectrum of produced compound (8-5) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) δ (ppm) 2.42(12H, s) 7.04 (2H, s) 7.65 (1H, t) 8.11 (2H, d) 8.52 (1H, s) 10.80 (2H,s)

Synthetic Example 21a Synthesis of Compound (8-6)

The compound was synthesized as in Synthetic example 1a-1 except that2,4-diamino-5,6,7,8-tetrahydroquinazoline and methyl m-methylbenzoatewere used as starting materials in place of2,4-diamino-6-methylpyrimidine and methyl benzoate, respectively, inSynthetic example 1a-1.

The NMR spectrum of produced compound (8-6) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) δ (ppm) 1.65-1.75(2H, m) 1.75-1.90 (2H, m) 2.40 (6H, s) 2.47-2.56 (2H, m) 2.80-2.87 (2H,m) 7.35-7.49 (4H, m) 7.71-7.88 (4H, m) 10.72 (1H, s) 10.78 (1H, s)

Synthetic Example 22a-1 Synthesis-1 of Mixture a Containing Compound(1-2), Compound (2-2), Compound (10-1), and Compound (10-2)

Synthesis was performed as in Synthetic example 5a except that a mixtureof methyl benzoate and methyl m-methylbenzoate was used as a startingmaterial in place of methyl m-methylbenzoate. Methyl m-methylbenzoate(21.7 g: 145 mmol), methyl benzoate (19.7 g: 145 mmol), and sodiummethoxide (26.1 g: 483 mmol) were added to a solution of2,4-diamino-6-methylpyrimidine (15 g: 121 mmol) in N-ethylpyrrolidone(105 mL), followed by stirring with heating at 40° C. for 3 hours. Thetemperature of the reaction system was decreased to room temperature.The reaction solution was poured into a liquid mixture of water (190mL), concentrated hydrochloric acid (63 mL), and ethyl acetate (40 mL)under ice cooling, and the solid component was collected by filtration.The resulting hydrochloride was added to saturated aqueous sodiumbicarbonate solution (120 mL) and ethyl acetate (300 mL), followed bystirring with heating for dissolution. The solution was cooled to roomtemperature to precipitate the product. The crude product was collectedby filtration and was dried at 80° C. under reduced pressure for 8 hoursto yield a mixture of compound (1-2), compound (2-2), compound (10-1),and compound (10-2) (product amount: 28 g, yield: 67%, water content:3.0%).

Synthetic Example 22a-2 Synthesis-2 of Mixture A Containing Compound(1-2), Compound (2-2), Compound (10-1), and Compound (10-2)

The crystals prepared in Synthetic example 22a-1 were dried at 170° C.under reduced pressure for 3 hours to give amorphous mixture A. Thewater content ratio of the mixture immediately after the drying was lessthan 0.5%.

Synthetic Example 23a Synthesis of mixture B containing Compound (1-2),Compound (2-2), Compound (10-1), and Compound (10-2)

A mixture of compound (1-2), compound (2-2), compound (10-1), andcompound (10-2) was synthesized as in Synthetic example 1a-1 except thata mixture of methyl benzoate (9.3 g) and methyl m-methylbenzoate (15.2g) was used as a starting material in place of methyl benzoate (23 g) inSynthetic example 1a-1. The content of compound (1-2) was decreased, andthe content ratio of compound (2-2) was increased, compared to those inSynthetic example 22a-1.

Synthetic Example 24a Synthesis of Mixture C

2,4-Diamino-6-chloropyrimidine (5.8 g: 40 mmol) and sodium methoxide(22.7 g) were sequentially added to t-butanol (51 mL) and methanol (9mL) under a nitrogen gas flow, followed by stirring with heating at 80°C. for 0.5 hours. The reaction solution was cooled to 70° C., and methylbenzoate (19.6 g: 96 mol) was dropwise added thereto, followed bystirring with heating at 70° C. for 6 hours. The reaction solution wascooled to 40° C., and 1-methoxy-2-propanol (45 mL) was added thereto.This solution was added to a liquid mixture of water (68 mL) and aceticacid (25.22 g) cooled with ice. Furthermore, water (200 mL) addedthereto, followed by stirring under ice cooling for 1 hour toprecipitate the product. The precipitated product was collected byfiltration and was washed with poured water to yield 8.3 g (yield: 60%)of the product. The product was identified as a mixture of compound(M-5a)/compound (M-6a)/compound (1-9) in a ratio of 1.5/3.5/95 (arearatio of HPLC) by HPLC.

Synthetic Example 25a Synthesis of Mixture D

2,4-Diamino-6-methylpyrimidine (7.4 g: 60 mmol) and sodium methoxide(11.3 g) were sequentially added to N-ethylpyrrolidone (30 mL) under anitrogen gas flow. Subsequently, methyl m-methylbenzoate (21.6 g: 144mol) was dropwise added thereto, followed by stirring with heating at40° C. for 3 hours. The reaction solution was added to a liquid mixtureof ethyl acetate (30 mL), water (75 mL), and hydrochloric acid (17.5 mL)cooled with ice, and water (100 mL) was further added thereto, followedby stirring under ice cooling for 1 hour to precipitate the product. Theprecipitated product was collected by filtration and was washed withpoured ethyl acetate, acetonitrile, and water to yield 15.1 g (yield:71%) of the product. The product was identified as a mixture of compound(M-3a)/compound (M-4a)/compound (2-2) by HPLC.

Synthetic Example 26a Synthesis of Compound (9-1)

The compound was synthesized in accordance with the method described inBioorg. Med. Chem. Lett., vol. 13, p. 217, 2003.

Synthetic Example 27a Synthesis of Compound (9-2)

The compound was synthesized in accordance with the method described inBioorg. Med. Chem. Lett., vol. 13, p. 217, 2003.

Synthetic Example 28a Synthesis of Compound (9-3)

The compound was synthesized in accordance with the method described inJournal of the Chemical Society, p. 41, 1947.

Synthetic Example 29a Synthesis of Compound (9-4)

The compound was synthesized in accordance with the method described inTetrahedron, vol. 57, p. 2787, 2001.

Synthetic Example 30a Synthesis of Compound (9-5)

The compound was synthesized in accordance with the method described inAngewandte Chemie, vol. 111, p. 2170, 1999.

Synthetic Example 31a Synthesis of Compound (9-13)

The compound was synthesized as in Synthetic example 1a-1 using compound(9-11) (commercial product) as a starting material in place of2,4-diamino-6-methylpyrimidine in Synthetic example 1a-1.

Synthetic Example 32a Synthesis of Compound (6-19)

The compound was synthesized as in Synthetic example 1a-1 except that2,4-diamino-6-methoxypyrimidine and methyl acetate were used as startingmaterials in place of 2,4-diamino-6-methylpyrimidine and methylbenzoate, respectively, in Synthetic example 1a-1. The solution afterthe reaction was poured into an aqueous acetic acid solution, followedby adjusting the solution to pH 6. The precipitated solid was collectedby filtration and was washed with poured MeOH/H₂O to yield compound(6-19).

The NMR spectrum of produced compound (6-19) is as follows. The NMRspectrum of produced compound (1-9) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) δ (ppm) 2.11 (3H,s) 2.26 (3H, s) 3.88 (3H, s) 7.10 (1H, s) 10.11 (1H, br) 10.50 (1H, br)

The water content ratios of the synthesized compounds were measured by aKarl-Fischer method.

Compound (1-2): water content ratio 3.8%

Compound (1-8): water content ratio 5.4%

Compound (1-9) (Synthetic example 3a-1): water content ratio 2.8%

Compound (1-9) (Synthetic example 3a-2): water content ratio 7.1%

Compound (1-9) (Synthetic example 3a-3): water content ratio 7.5%

Compound (1-9) (Synthetic example 3a-4): water content ratio <0.5%

Compound (2-1): water content ratio 5.5%

Compound (2-2): water content ratio 3.4%

Compound (2-4): water content ratio 1.3%

Compound (2-8): water content ratio 1.8%

Compound (2-9): water content ratio 3.2%

Compound (5-1): water content ratio 3.1%

Compound (5-2): water content ratio 0.8%

Compound (5-7): water content ratio 9.1%

Compound (5-8): water content ratio 3.1%

Compound (6-13): water content ratio 1.2%

Compound (6-15): water content ratio 2.7%

Compound (6-16): water content ratio 2.8%

Compound (6-19): water content ratio 0.7%

Compound (7-2): water content ratio 3.1%

Compound (8-2): water content ratio 1.0%

Compound (8-5): water content ratio 2.6%

Compound (8-6): water content ratio 3.1%

Example 2a-1 Production of Cellulose Acylate Film Preparation ofCellulose Acylate Solution for Film Formation

The exemplary compounds shown in the table below were mixed withcellulose acylate resins having degrees of acetyl substitution inproportions based on 100 parts by mass of the cellulose acylate resinsshown in the table, and the compounds were each dissolved in a solventcomposed of 396 parts by mass of methylene chloride and 59 parts by massof methanol to prepare a cellulose acylate (specifically, celluloseacetate) solution.

(Casting)

The cellulose acylate solutions prepared above were each casted with aglass plate casting machine, followed by drying with hot air having acharge air temperature of 70° C. for 6 minutes. The films were peeledoff from the glass plates, were fixed to frames, and were dried with hotair having a charge air temperature of 100° C. for 10 minutes and thenwith hot air having a charge air temperature of 140° C. for 20 minutesto produce cellulose acylate films each having a thickness of 65 μm.

Subsequently, the resulting films were each stretched in cross-directionby an stretched ratio of 30% under conditions of a temperature of 200°C. and a drawing rate of 30%/min to produce cellulose acylate films eachhaving a thickness of 50 μm.

An additive-free film was produced as a comparative example film.Separately, a comparative example film containing an additive ofcomparative compound 1 having a structure shown below was produced.

(Evaluation of Optical Characteristics)

The prepared films of examples and comparative examples were eachhumidified at a relative humidity of 60% at 25° C. for 24 hours.Retardations at a wavelength of 590 nm were measured from the directionperpendicular to the film surface and the directions tilted from thefilm plane normal by 10° in the range from +50° to −50° using a slowaxis as the rotation axis at a relative humidity of 60% at 25° C. withan automatic birefringence meter (KOBRA-21ADH: manufactured by OjiScientific Instruments Co., Ltd.), and the in-plane retardation value(Re) and the thickness retardation value (Rth) were calculated.

The results are shown in the table below.

In order to evaluate the changes in the retardation value depending onhumidity, the humidity dependency (ΔRe) of Re and the humiditydependency (ΔRth) of Rth were calculated from the Re and the Rth (Re[25° C., RH10%] and Rth [25° C., RH10%], respectively) determined as inabove except that humidification was performed at a relative humidity of10% at 25° C. for 2 hours and the Re and the Rth (Re [25° C., RH80%] andRth [25° C., RH80%], respectively) determined as in above except thathumidification was performed at a relative humidity of 80% at 25° C. for12 hours.

The results are shown as ΔRe and ΔRth in the table below.

The humidity dependency was evaluated by the following evaluationcriteria.

[Evaluation Criteria of ΔRe]

⊚: ΔRe<10

◯: 10≦ΔRe<11

: 11≦ΔRe<16

x: 16≦ΔRe

[Evaluation Criteria of ΔRth]

⊚: ΔRth<18

◯: 18≦ΔRth<21

: 21≦ΔRth<25

x: 25≦ΔRth

TABLE 4 Cellulose acylate Additive resin Optical characteristics of filmFilm Amount Degree of acetyl Re Rth Δ Re Δ Rth Δ Re Δ Rth No. Compound[Parts by mass] substitution [nm] [nm] [nm] [nm] Evaluation EvaluationRemarks 101a 1-1 4 2.42 65.1 160.3 6.7 13.1 ⊚ ⊚ Example 102a 1-2 4 2.4264.3 162.8 6.5 13.4 ⊚ ⊚ Example 103a 1-3 4 2.42 67.3 164.9 7.1 13.9 ⊚ ⊚Example 104a 1-4 4 2.42 66.4 159.3 7.6 14.3 ⊚ ⊚ Example 105a 1-5 4 2.4265.9 161 8.1 15.7 ⊚ ⊚ Example 106a 1-6 4 2.42 64.2 163.5 8.4 16.2 ⊚ ⊚Example 107a 1-7 4 2.42 67.1 165.3 8.9 17.5 ⊚ ⊚ Example 108a 1-8 4 2.4265.2 163.1 7.5 14.1 ⊚ ⊚ Example 109a  1-9*1 4 2.42 62.9 161.4 6.8 13.0 ⊚⊚ Example 110a  1-10 4 2.42 64.8 161.9 9.7 18.8 ⊚ ⊚ Example 111a  1-11 42.42 67.3 167.2 8.2 16.2 ⊚ ⊚ Example 112a 2-1 4 2.42 66.1 159.1 6.9 13.3⊚ ⊚ Example 113a 2-2 4 2.42 52.9 142.1 6.6 12.8 ⊚ ⊚ Example 114a 2-4 42.42 66.0 165.8 7.6 14.7 ⊚ ⊚ Example 115a 2-8 4 2.42 71.2 186.0 9.7 19.6⊚ ∘ Example 116a 2-9 4 2.42 63.9 162.7 7.2 15.9 ⊚ ⊚ Example 117a 3-3 42.42 67.9 169.1 8.2 16.5 ⊚ ⊚ Example 118a 3-8 4 2.42 66.8 164.3 7.9 15.1⊚ ⊚ Example 119a 4-1 4 2.42 64.2 164.5 7.4 15.8 ⊚ ⊚ Example 120a 4-8 42.42 65.3 166.4 7.8 16.2 ⊚ ⊚ Example 121a 5-1 4 2.42 64.3 166.2 7.2 15.6⊚ ⊚ Example 122a 5-8 4 2.42 67.2 167.1 7.8 16.3 ⊚ ⊚ Example 123a 6-2 42.42 68.2 166.9 8.5 16.7 ⊚ ⊚ Example 124a 6-4 4 2.42 64.5 164.8 8.4 16.3⊚ ⊚ Example 125a 6-5 4 2.42 65.9 166.2 8.1 16.0 ⊚ ⊚ Example 126a 6-6 42.42 62.0 162.5 10.1 19.7 ∘ ∘ Example 127a 6-7 4 2.42 68.4 165.2 10.219.8 ∘ ∘ Example 128a  6-13 4 2.42 73.5 167.0 10.8 20.3 ∘ ∘ Example 129a 6-14 4 2.42 66.7 164.5 10.6 21.0 ∘ Δ Example 130a  6-16 4 2.42 64.2160.1 7.4 15.6 ⊚ ⊚ Example 131a 7-1 4 2.42 71.0 167.0 7.1 16.8 ⊚ ⊚Example 132a 7-2 4 2.42 68.8 176.7 8.6 17.7 ⊚ ⊚ Example 133a 7-3 4 2.4269.4 170.2 8.7 18.0 ⊚ ∘ Example 134a 7-5 4 2.42 64.5 162.5 10.5 20.3 ∘ ∘Example 135a 7-7 4 2.42 69.1 165.7 7.4 16.5 ⊚ ⊚ Example 136a 7-9 4 2.4272.0 168.3 8.1 17.2 ⊚ ⊚ Example 137a 8-1 4 2.42 60.4 144.6 10.3 21.6 ∘ ΔExample 138a 8-2 4 2.42 55.3 135.3 11.1 22.4 Δ Δ Example 139a 8-3 4 2.4256.5 142.9 10.4 21.3 ∘ Δ Example 140a 8-4 4 2.42 58.3 143.9 10.8 22.4 ∘Δ Example *1: Compound 1-9 produced in Synthetic example 3a-1

TABLE 5 Cellulose acylate Additive resin Optical characteristics of filmFilm Amount Degree of acetyl Re Rth Δ Re Δ Rth Δ Re Δ Rth No. Compound[Parts by mass] substitution [nm] [nm] [nm] [nm] Evaluation EvaluationRemarks 141a 8-5 4 2.42 54.9 137.3 10.7 22.0 ∘ Δ Example 142a 8-6 4 2.4259.2 132.2 11.5 22.0 Δ Δ Example 143a  9-13 4 2.42 58.2 134.1 10.8 21.9Δ Δ Example 144a 1-2 2 2.42 64.4 161.1 6.8 13.3 ⊚ ⊚ Example 2-2 2 145aMixture A 4 2.42 64 162.2 6.7 13.3 ⊚ ⊚ Example 146a Mixture B 4 2.4263.8 161.4 6.8 13.4 ⊚ ⊚ Example 147a Mixture C 4 2.42 60.4 156.4 7.216.2 ⊚ ⊚ Example 148a Mixture D 4 2.42 59.2 152.6 7.3 17.1 ⊚ ⊚ Example149a  1-9*1 3.5 2.42 64.1 164.2 7.0 15.7 ⊚ ⊚ Example  6-16 0.5 150a 2-93.8 2.42 62.2 161.1 7.3 16.7 ⊚ ⊚ Example  6-17 0.2 151a  1-9*1 3.8 2.4264.3 163.1 7.1 16.0 ⊚ ⊚ Example 1-8 0.2 152a  1-9*1 6 2.42 67.2 166.14.8 12.1 ⊚ ⊚ Example 153a 2-9 8 2.42 68.2 167.8 4.1 11.8 ⊚ ⊚ Example154a 2-9 12 2.42 71.0 172.3 3.6 8.8 ⊚ ⊚ Example 155a Mixture B 6 2.4268.2 169.1 4.7 12.0 ⊚ ⊚ Example 156a — 0 2.42 44.7 126 16.8 26.4 x xComparative example 157a Comparative 4 2.42 94.2 201.3 11.8 22.6 Δ ΔComparative compound 1 example *1: Compound 1-9 produced in Syntheticexample 3a-1

The results shown in the tables above demonstrate that all polymer filmsof examples of the present invention have increased retardation bycontaining the compounds of Formula (1) and also have reduced humiditydependency of retardation compared to the comparative example filmhaving increased retardation by containing a triazine ring compound.

It is demonstrated that the effect of reducing the humidity dependencyof retardation is relatively low in compounds having a substituent atthe 5-position of the pyrimidine ring so as to be sterically bulky andhave low flatness, such as compounds (8-6) and (9-13).

Example 2a-2 Production of Cellulose Acylate Film

Cellulose acetate films were formed as in Example 2a-1 except that thestretching was performed at 180° C. instead of 200° C., and the opticalcharacteristics were evaluated.

The humidity dependency was evaluated by the following evaluationcriteria.

[Evaluation Criteria of ΔRe]

◯: ΔRe<10

: 10≦ΔRe<15

x: 15≦ΔRe

[Evaluation Criteria of ΔRth]

◯: ΔRth<22

: 22≦ΔRth<26

x: 26≦ΔRth

TABLE 6 Cellulose acylate Additive resin Optical characteristics of filmFilm Amount Degree of acetyl Re Rth Δ Re Δ Rth Δ Re Δ Rth No. Compound[Parts by mass] substitution [nm] [nm] [nm] [nm] Evaluation EvaluationRemarks 201a 1-1 2 2.86 5.2 44.3 11.2 24.1 Δ Δ Example 202a 1-2 4 2.8616.0 71.0 7.9 17.2 ∘ ∘ Example 203a 2-1 4 2.86 15.3 68.1 8.1 15.4 ∘ ∘Example 204a 2-2 4 2.86 14.8 66.9 8.3 15.7 ∘ ∘ Example 205a 2-4 4 2.8611.0 65.2 7.9 17.1 ∘ ∘ Example 206a 3-3 4 2.86 17.9 76.1 9.2 18.4 ∘ ∘Example 207a 3-9 4 2.86 17.5 67.9 8.9 19.0 ∘ ∘ Example 208a 4-9 4 2.8616.4 69.3 9.1 20.5 ∘ ∘ Example 209a  5-11 4 2.86 17.6 68.4 9.2 21.1 ∘ ∘Example 210a 6-3 4 2.86 20.2 72.5 9.8 21.4 ∘ ∘ Example 211a 7-2 4 2.8619.4 81.8 8.6 18.2 ∘ ∘ Example 212a — 0 2.86 −10.4 13.0 12.7 27.5 Δ xComparative example 213a Comparative 4 2.86 39.5 102.0 12.2 24.6 Δ ΔComparative compound 1 example

Example 2a-3 Production of Cellulose Acylate Film

(Preparation of Cellulose Acylate Solution for Film Formation)

The exemplary compounds shown in the table below were mixed withcellulose acylate resins having degrees of acetyl substitution inproportions based on 100 parts by mass of the cellulose acylate resinsshown in the table, and the compounds were each dissolved in a solventcomposed of 396 parts by mass of methylene chloride and 59 parts by massof methanol to prepare a cellulose acylate (specifically, celluloseacetate) solution.

(Casting)

The cellulose acylate solutions prepared above were each casted with aglass plate casting machine, followed by drying with hot air having acharge air temperature of 70° C. for 6 minutes. The films were peeledoff from the glass plates, were fixed to frames, and were dried with hotair having a charge air temperature of 100° C. for 10 minutes and thenwith hot air having a charge air temperature of 140° C. for 20 minutesto produce cellulose acylate films each having a thickness of 55 μm.

An additive-free film was produced as a comparative example film.Separately, a comparative example film containing an additive ofcomparative compound 1 was produced.

(Evaluation of Optical Characteristics)

Optical characteristics were evaluated as in Example 2a-1, and thehumidity dependency was evaluated by the following evaluation criteria.

[Evaluation Criteria of ΔRth]

◯: ΔRth<15

: 15≦ΔRth<20

x: 20≦ΔRth

TABLE 7 Cellulose acylate Additive resin Optical characteristics of filmFilm Amount Degree of acetyl Re Rth Δ Re Δ Rth Δ Rth No. Compound [Partsby mass] substitution [nm] [nm] [nm] [nm] Evaluation Remarks 301a  1-9*16 2.86 2.4 90.3 0.7 13.1 ∘ Example 302a 2-2 6 2.86 1.7 83.8 0.2 12.3 ∘Example 303a 2-9 6 2.86 1.6 89.7 0.3 13.4 ∘ Example 304a 7-2 6 2.86 2.392.0 0.6 12.8 ∘ Example 305a Mixture A 6 2.86 2.4 91.1 0.5 12.7 ∘Example 306a — 0 2.86 2.1 31.1 0.0 22.3 x Comparative example 307aComparative 6 2.86 3.9 137.3 0.8 15.3 Δ Comparative compound 1 example*1: Compound 1-9 produced in Synthetic example 3a-1

Example 2a-4 Production of Cellulose Acylate Film

Cellulose acetate films were produced as in Example 2a-1, and theoptical characteristics were evaluated.

TABLE 8 Cellulose acylate Additive resin Optical characteristics of filmFilm Amount Degree of acetyl Re Rth Δ Re Δ Rth No. Compound [Parts bymass] substitution [nm] [nm] [nm] [nm] Remarks 401a 9-1 2 2.42 47.3136.4 11.2 23.6 Example 402a 9-2 2 2.42 41.1 118.6 11.5 23.8 Example403a 9-3 2 2.42 39.4 112.6 11.7 23.4 Example 404a 9-4 2 2.42 31.9 115.110.3 21.4 Example 405a 9-5 2 2.42 36.1 113.8 10.4 22 Example 156a — 02.42 44.7 126 16.8 26.4 Comparative example 406a Comparative 2 2.42 70.8180.8 12 26.4 Comparative compound 1 example

The results shown in the tables above demonstrate that all polymer filmsof examples of the present invention have increased retardation bycontaining the compounds of Formula (1) and also have reduced humiditydependency of retardation compared to the comparative example filmhaving increased retardation by containing a triazine ring compound.

Example 2a-5 Production of Cellulose Acylate Film

Cellulose acetate films were produced as in Example 2a-1, and theoptical characteristics were evaluated.

Films were produced as in Example 2a-1 except that the additive was eachmixture E-1 and E-2 composed of exemplary compound (1-2) and a triazinecompound shown below at a compositional ratio (mass ratio) of 1:1, andthe optical characteristics were measured. The results are shown in thetable below together with the results of film 102 of Example 2a-1 andfilm 156 of a comparative example.

TABLE 9 Cellulose acylate Additive resin Optical characteristics of filmFilm Amount Degree of acetyl Re Rth Δ Re Δ Rth No. Compound [Parts bymass] substitution [nm] [nm] [nm] [nm] Remarks 102a 1-2 4 2.42 64.3162.8 6.5 13.4 Example 501a Mixture E-1 4 2.42 95.3 200.9 11.6 22.6Example 502a Mixture E-2 4 2.42 96.3 211.4 12.0 22.1 Example 156a — 02.42 44.7 126.0 16.8 26.4 Comparative example

The results shown in the table demonstrate that the use of a compound(exemplary compound (1-2)) represented by Formula (1) together with atriazine ring compound enhances the effect of increasing theretardation, but reduces the effect of reducing the humidity dependencyof retardation. The results demonstrate that the effect of reducing thehumidity dependency shown in Examples of the present invention cannot beachieved by a retardation enhancer composed of a molecular complexhaving a keto-enol tautomeric structure as a constituent elementdisclosed in Japanese Patent Laid-Open No. 2004-109410 (PatentLiterature 1) and a retardation enhancer composed of a disk-shapedcompound having a 1,3,5-triazine ring described in Japanese PatentLaid-Open No. 2001-166144 (Patent Literature 2) and Japanese PatentLaid-Open No. 2003-344655 (Patent Literature 3).

Example 3a Production of Cellulose Acylate Film

(Preparation of Cellulose Acylate Solution for Film Formation)

The composition shown below was put in a mixing tank, followed bystirring to dissolve each component to prepare a cellulose acylatesolution 301.

TABLE 10 Composition of cellulose acylate solution 301 Cellulose acetatehaving a degree of 100.0 parts by mass acetyl substitution of 2.43 and adegree of polymerization of 340: Compound (2-2): 4.0 parts by massMethylene chloride (first solvent): 402.0 parts by mass Methanol (secondsolvent): 60.0 parts by mass

(Casting, Stretching)

The cellulose acylate solution 301 was casted with a band castingmachine, followed by drying until the remaining solvent content reached40%. The formed web film was peeled off from the band. When theremaining solvent content reached 20% under conditions of 140° C., thefilm was stretched in cross-direction by a stretch ratio of 30% with atenter and was then maintained at 130° C. for 3 minutes. Subsequently,the clips holding the film were removed, and the film was dried at 130°C. for 30 minutes to produce a cellulose acylate film 301. The thicknessof the film was 60 μm.

An additive-free film (cellulose acylate film 302) was produced as acomparative example film. Separately, a comparative example film(cellulose acylate film 303) containing an additive of comparativecompound 1 was produced.

(Evaluation of Optical Characteristics)

The optical characteristics were evaluated as in Example 2a-1. In thecellulose acylate film 301 containing a compound of the presentinvention, the humidity dependency of retardation was reduced comparedto those of cellulose acylate films 301 and 302.

Example 4a Production of Cellulose Acylate Film

Cellulose acetate films containing a mixture (R-1), (R-2), and (R-3) asan additive were produced as in Example 2a-1, and the opticalcharacteristics of the films were evaluated.

Cellulose acetate films were produced as in Example 2a-1 except that thedegree of substitution of cellulose acylate, the type and amount ofadditive, the stretching temperature, the stretching ratio, and thethickness of each film were as shown in the following table.

Optical characteristics were evaluated as in Example 1a.

TABLE 11 Cellulose Optical characteristics Additive Other additiveacylate resin of film Amount Amount Degree of acetyl Stretching Re Rth ΔRe Δ Rth Film No. Mixture [Parts by mass] Compound [Parts by mass]substitution condition [nm] [nm] [nm] [nm] 503a R-1 4 Polycondensation10 2.42 180° C. 44 109 6.5 11.8 (Example) ester B 30% 504a R-3 4Polycondensation 10 2.42 180° C. 46 112 6.3 11.8 (Example) ester B 30%505a R-6 4 Polycondensation 10 2.42 180° C. 46 113 6.1 12 (Example)ester B 30% 506a R-7 4 Polycondensation 10 2.42 180° C. 48 114 5.7 12(Example) ester B 30% 507a R-9 4 Polycondensation 10 2.42 180° C. 47 1136 12.1 (Example) ester B 30% 508a — 0 Polycondensation 10 2.42 180° C.35 99 9.3 22.7 (Example) ester B 30%In the table, polycondensation ester B is a copolymer of adipicacid/ethanediol in a ratio of 50/50.

The films containing mixtures (R-2), (R-4), (R-5), (R-8), (R-10),(R-11), and (R-12) to (R-15) and mixture C were similarly evaluated, andreductions in humidity dependency of retardation were confirmed.

Example 5a Production of Cellulose Acylate Film

A cellulose acetate film was produced as in Example 2a-1 using themixture (A) and compound (1-9) as additives.

Cellulose acylate films were produced as in Example 2a-1 except that thedegree of substitution of cellulose acylate was 2.42 as a degree ofacetyl substitution and the amount of each additive was 4% by mass,though the stretching temperature, the stretching ratio, and thethickness of each film were the same as those in Example 2a-1.

Several films were produced on different days and using mixture A andcompound (1-9) different in lots.

(Evaluation of Optical Characteristics)

Optical characteristics were evaluated as in Example 2a-1.

TABLE 12 Additive Optical characteristics of film Form Δ Re Δ Rth (WaterRe [nm] Rth [nm] Variation Synthesis content Sample [nm] Standard [nm]Standard of optical Film No. Species method ratio) number Averagedeviation Average deviation characteristec 509a Mixture A SyntheticHydrate 6 68.2 1.8 174.1 3.8 ∘ (Example) example 22a-1 (3.0%)   510aMixture A Synthetic Amorphous 6 69.4 4.2 176.2 7.1 Δ (Example) example22a-2 (<0.5%) 511a Compound Synthetic Hydrate 6 65.5 1.7 171.5 4.0 ∘(Example) 1-9 example 3a-2 (7.1%) 512a Compound Synthetic Amorphous 665.4 5.0 173.4 8.5 Δ (Example) 1-9 example 3a-4 (<0.5%) ″∘″ means astandard deviation of less than 5%, and ″Δ″ means a standard deviationof not less than 5%.

The results shown in the table demonstrate that the opticalcharacteristics of films highly variations when the films are formedusing anhydrides of compound (1-9) and mixture A prepared by drying withheating under reduced pressure in Synthetic examples 3-4 and 22-2. Thisis believed that the compound (1-9) or each compound in the mixture Aisolated in the anhydride form absorbs moisture during storage to varythe actual content ratio if an equal amount of anhydride is added forformation of films.

In contrast, the films formed using hydrates prepared in Syntheticexamples 3-2 and 22-1 show small variations to indicate excellentstability of quality. This is believed that the water content ratio incrystals prepared in the hydrate form does not vary with the passage oftime.

Example 6a Evaluation in Change of Water Content Ratio

Each compound (0.5 g) shown in the following table was left in athermostatic and humidifying chamber at 25° C. and 80% RH for 7 days,and then water content ratio was measured by a Karl-Fischer method.

TABLE 13 Water content Water content ratio of at ratio of at SynthesisInitial water 25° C. and 80% 25° C. and 10% Compound Form method contentratio RH for 7 days RH for 7 days Example (1-9) Hydrate Synthetic 2.82.9 2.7 example 3a-1 Example (1-9) Hydrate Synthetic 7.1 7.2 7.2 example3a-2 Example (1-9) Amorphous Synthetic <0.5 6.6 1.0 example 3a-4 Example(Mixture A) Hydrate Synthetic 3.1 3.4 3.3 example 22a-1 Example (MixtureA) Amorphous Synthetic <0.5 6.5 1.3 example 22a-2 Example (2-2) HydrateSynthetic 3.4 3.4 3.2 example 5a Example (2-2) Amorphous * <0.5 3.1 1.2Example (7-2) Hydrate Synthetic 3.1 3.2 3.0 example 15a Example (7-2)Amorphous * <0.5 2.8 0.9 * An amorphous compound was prepared as inSynthetic example 3a-4 by drying the compound through heating to themelting point or higher under reduced pressure and then quenching.

The results shown in the table demonstrate that the compound of thepresent invention in the hydrate form maintains a constant water ratiocontent regardless of a change in humidity and that the compound in theamorphous form absorbs moisture to vary the water content ratiodepending on environmental humidity despite a low initial water contentratio of the amorphous form.

Example 7a Evaluation of Solution Stability

Each compound (1 part by mass) shown in the following table wasdissolved in methylene chloride (87 parts by mass) and methanol (13parts by mass). The solution was left to stand in a pressure resistantvessel at 80° C. for 66 hours, and then the residual ratio of thecompound was quantitatively measured by liquid chromatography. Theresults are shown in the following table.

TABLE 14 Compound Residual ratio (%) Example (1-1) >95 Example (1-2) >95Example (1-4) >95 Example (1-9) >95 Example (2-1) >95 Example (2-2) >95Example (2-4) >95 Example (2-9) >95 Comparative (A-1) 58 exampleComparative (A-2) 54 example

Comparative compound A-1: The compound was synthesized in accordancewith the method described in Gazzetta Chimica Italiana (1935), 65,566-88.

Comparative compound A-2: The compound is described in Japanese PatentLaid-Open No. 2007-138119 and was synthesized in accordance with themethod described in Gazzetta Chimica Italiana (1935), 65, 566-88.

The results shown in the table demonstrate that the compound group A ofthe present invention shows high solution stability.

Example 1b Synthetic Example of Compound in Compound Group B Representedby Formula (I) Synthetic Example 1b Synthesis of Compound (Ib-3)

Methyl m-methylbenzoate (10.7 g: 71 mmol) and sodium methoxide (7.7 g:143 mmol) were added to a solution of 2,4-diaminopyrimidine (10 g: 71mmol) in N-ethylpyrrolidone (70 mL), followed by stirring with heatingat 40° C. for 1 hour. The temperature of the reaction system wasdecreased to room temperature. The reaction solution was poured in adiluted hydrochloric acid for neutralization, followed by extractionwith ethyl acetate. The resulting organic layer was washed withsaturated brine and was dried over anhydrous sodium sulfate. Thedesiccant was removed, and the solvent was distilled off. The crudeproduct was purified by silica gel column chromatography (eluent: ethylacetate) to yield compound (Ib-3). The NMR spectrum of produced compound(Ib-3) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) 10.02 (1H, s)8.00 (1H, d) 7.75-7.68 (2H, m) 7.40-7.33 (2H, m) 6.84 (2H, br) 6.20 (1H,d) 2.35 (3H, s)

Synthetic Example 2b Synthesis of Compound (Ib-9)

The compound was synthesized as in Synthetic example 1b except that6-methyl-2,4-diaminopyrimidine and methyl benzoate were used as startingmaterials in place of 2,4-diaminopyrimidine and methyl m-methylbenzoate,respectively, in Synthetic example 1b. The NMR spectrum of producedcompound (Ib-9) is as follows (water content ratio: 2.45%).

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) 10.27 (1H, br)7.97-7.88 (2H, m) 7.60-7.44 (3H, m) 6.70 (2H, br) 6.07 (1H, s) 2.18 (3H,s)

Synthetic Example 3b Synthesis of Compound (Ib-11)

The compound was synthesized as in Synthetic example 1b except that6-methyl-2,4-diaminopyrimidine was used as a starting material in placeof 2,4-diaminopyrimidine in Synthetic example 1b. The NMR spectrum ofproduced compound (Ib-11) is as follows (water content ratio: 2.8%).

¹H-NMR (solvent: CDCl₃, standard: tetramethylsilane) 7.90 (1H, s)7.75-7.64 (2H, m) 7.34-7.27 (2H, m) 6.07 (1H, s) 5.80 (2H, br) 2.37 (3H,s) 2.21 (3H, s)

Synthetic Example 4b Synthesis of Compound (Ib-25)

The compound was synthesized as in Synthetic example 1b except that6-methoxy-2,4-diaminopyrimidine and methyl benzoate were used asstarting materials in place of 2,4-diaminopyrimidine and methylm-methylbenzoate in Synthetic example 1b. The NMR spectrum of producedcompound (Ib-25) is as follows (water content ratio: 0.8%).

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) 10.29 (1H, s)7.91-7.86 (2H, m) 7.60-7.25 (3H, m) 6.60 (2H, br) 5.51 (1H, s) 3.73 (3H,s)

Synthetic Example 5b Synthesis of Compound (Ib-78)

Compound (Ib-78) was synthesized as in Synthetic example 1b. The NMRspectrum of produced compound (Ib-78) is as follows.

¹H-NMR (solvent: dimethyl sulfoxide, standard: tetramethylsilane) 10.39(1H, s) 8.18 (1H, d) 7.83-7.75 (2H, m) 7.42-7.35 (3H, m) 6.39 (2H, br)2.38 (3H, s)

Synthetic Example 6b Synthesis of Compound (Ib-84)

Compound (Ib-84) was synthesized as in Synthetic example 2b. The NMRspectrum of produced compound (Ib-84) is as follows (water contentratio: 0.3%).

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) 10.46 (1H, s)7.98 (2H, d) 7.64-7.48 (3H, m) 7.30 (1H, s) 6.29 (2H, br) 2.25 (3H, s)

Synthetic Example 7b Synthesis of Compound (Ib-86)

Compound (Ib-86) was synthesized as in Synthetic example 3b. The NMRspectrum of produced compound (Ib-86) is as follows (water contentratio: 0.3%).

¹H-NMR (solvent: CDCl₃, standard: tetramethylsilane) 8.29 (1H, br)7.70-7.63 (2H, M) 7.58 (1H, S) 7.40-7.35 (2H, M) 4.93 (2H, BR) 2.43 (3H,S) 2.39 (3H, S)

Synthetic Example 8b Synthesis of Compound (Ib-100)

Compound (Ib-100) was synthesized as in Synthetic example 4b. The NMRspectrum of produced compound (Ib-100) is as follows (water contentratio: 2.0%).

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) 10.42 (1H, s)7.96 (2H, d) 7.65-7.45 (3H, m) 6.85 (1H, s) 6.40 (2H, br) 3.82 (3H, s)

Synthetic Example 9b Synthesis of Compound (Ib-159)

The compound was synthesized as in Synthetic example 4b except that6-chloro-2,4-diaminopyrimidine was used as a starting material in placeof 6-methoxy-2,4-diaminopyrimidine in Synthetic example 4b. The NMRspectrum of produced compound (Ib-159) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) 10.60 (1H, s)7.92 (2H, d) 7.60-7.45 (3H, m) 7.20 (2H, br) 6.21 (1H, s)

Synthetic Example 10b Synthesis of Compound (Ib-161)

The compound was synthesized as in Synthetic example 4b except that6-chloro-2,4-diaminopyrimidine was used as a starting material in placeof 6-methoxy-2,4-diaminopyrimidine in Synthetic example 4b. The NMRspectrum of produced compound (Ib-161) is as follows.

¹H-NMR (solvent: d6-DMSO, standard: tetramethylsilane) 10.88 (1H, s)7.96 (2H, d) 7.63-7.48 (3H, m) 7.42 (1H, s) 6.90 (2H, br)

Synthetic Example 11b Synthesis of Compound (IIb-6)

Compound (IIb-6) was synthesized by reference to the description inOrganic and Biomolecular Chemistry, 2007, Vol. 5, No. 10, 1577-1585.

Synthetic Example 12b Synthesis of Compound (IIb-9)

Compound (IIb-9) was synthesized by reference to the description inYakugaku Zasshi, 1951, Vol. 71, 315-317.

Synthetic Example 13b Synthesis of Compound (IIb-14)

Compound (IIb-14) was synthesized by reference to the description inMerck and Co., Inc., U.S. Pat. No. 4,144,338 A1, 1979.

Synthetic Example 14b Synthesis of Compound (IIb-16)

Compound (IIb-16) was synthesized by reference to the description inJournal of the American Chemical Society, 1947, Vol. 69, 1147-1148.

Synthetic Example 15b Synthesis of Compound (IIIb-1)

Compound (IIIb-1) was synthesized by reference to the description inBioorganic and Medicinal Chemistry, 1998, Vol. 9, No. 6, 643-660.

Synthetic Example 16b Synthesis of Compound (IIIb-6)

Compound (IIIb-6) was synthesized as in synthesis of compound (Ib-3)from diaminopyrimidine synthesized by reference to the description inChemical & Pharmaceutical Bulletin, 1981, Vol. 29, No. 4, 948-954.

Synthetic Example 17b Synthesis of Mixture b-A

2,4-Diamino-6-chloropyrimidine (5.8 g: 40 mmol) and sodium methoxide(22.7 g) were sequentially added to t-butanol (51 mL) and methanol (9mL) under a nitrogen gas flow, followed by stirring with heating at 80°C. for 0.5 hours. The reaction solution was cooled to 70° C., and methylbenzoate (19.6 g: 96 mol) was dropwise added thereto, followed bystirring with heating at 70° C. for 6 hours. The reaction solution wascooled to 40° C., and 1-methoxy-2-propanol (45 mL) was added thereto.The solution was added to a liquid mixture of water (68 mL) and aceticacid (25.22 g) cooled with ice. Furthermore, water (200 mL) was addedthereto, followed by stirring under ice cooling for 1 hour toprecipitate the product. The precipitated product was collected byfiltration and was washed with poured water to yield 8.3 g (yield: 60%)of the product. The product was identified as a mixture of compound(Ib-25)/compound (Ib-100)/reference compound (3) described below in aratio of 6.5/5.5/88 by HPLC.

Example 1b Preparation of Cellulose Acylate Solution for Film Formation(Preparation of Cellulose Acylate Solution for Film Formation)

The exemplary compounds shown in the table below were mixed withcellulose acylate resins having degrees of substitution with acetylgroups in proportions based on 100 parts by mass of the celluloseacylate resins shown in the table, and the compounds were each dissolvedin a solvent composed of 396 parts by mass of methylene chloride and 59parts by mass of methanol to prepare a cellulose acylate (specifically,cellulose acetate) solution.

(Casting)

The cellulose acylate solutions prepared above were each casted with aglass plate casting machine, followed by drying with hot air having acharge air temperature of 70° C. for 6 minutes. The films were peeledoff from the glass plates, were fixed to frames, and were dried with hotair having a charge air temperature of 100° C. for 10 minutes and thenwith hot air having a charge air temperature of 140° C. for 20 minutesto produce cellulose acylate films each having a thickness of 65 μm.

Subsequently, the resulting films were each stretched in cross-directionby a stretch ratio of 30% under conditions of a temperature of 200° C.and a drawing rate of 30%/min to produce cellulose acylate films eachhaving a thickness of 50 μm.

An additive-free film was produced as a comparative example film.Separately, a comparative example film containing an additive ofcomparative compound 1 having a structure shown below was produced.

Films containing any one of exemplary compounds shown in the table belowand any one of reference compounds 1 to 3 having structures shown belowas additives were produced. The reference compounds can be representedby Formulae (6) and (7).

(Evaluation of Optical Characteristics)

The prepared sample films were each humidified at a relative humidity of60% at 25° C. for 24 hours. Retardation at a wavelength of 590 nm weremeasured from the direction perpendicular to the film surface and thedirections tilted from the film plane normal by 10° in the range from+50° to −50° using a slow axis as the rotation axis at a relativehumidity of 60% at 25° C. with an automatic birefringence meter(KOBRA-21ADH: manufactured by Oji Scientific Instruments Co., Ltd.), andthe in-plane retardation value (Re) and the thickness retardation value(Rth) were calculated.

The results are shown in the table below.

In order to evaluate the changes in the retardation value depending onhumidity, the humidity dependency (ΔRe) of Re and the humiditydependency (ΔRth) of Rth were calculated from the Re and the Rth (Re[25° C., RH10%] and Rth [25° C., RH10%], respectively) determined as inabove except that humidification was performed at a relative humidity of10% at 25° C. for 2 hours and the Re and the Rth (Re [25° C., RH80%] andRth [25° C., RH80%], respectively) determined as in above except thathumidification was performed at a relative humidity of 80% at 25° C. for12 hours.

The results are shown as ΔRe and ΔRth in the tables below.

TABLE 15 Film No. Cellulose acylate Optical characteristics (Example/Additive resin of film Comparative Amount Degree of acetyl Re Rth Δ Re ΔRth example) Compound [Parts by mass] substitution [nm] [nm] [nm] [nm]101b (lb-1) 4 2.42 55.3 135.3 9.2 17.9 (Example) 102b (lb-76) 4 2.4254.1 129.8 9.2 17.6 (Example) 103b (lb-9) 4 2.42 53.2 130.8 9.3 18.1(Example) 104b (lb-84) 4 2.42 49 131.2 9.3 18.3 (Example) 105b (lb-11) 42.42 58.2 136.5 9.4 18.5 (Example) 106b (lb-86) 4 2.42 49.3 134.2 9.518.6 (Example) 107b (lb-3) 4 2.42 51.2 132.6 9.7 19.2 (Example) 108b(lb-78) 4 2.42 50.8 134.5 9.7 19 (Example) 109b (lb-25) 4 2.42 53.6132.1 9.8 19.1 (Example) 110b (lb-100) 4 2.42 55.8 130.9 9.7 19(Example) 111b (lb-27) 4 2.42 51.9 138.4 9.6 19.2 (Example) 112b(lb-102) 4 2.42 47.6 132.6 9.6 19.4 (Example) 113b (lb-49) 4 2.42 55.4128.6 9.7 19.4 (Example) 114b (lb-124) 4 2.42 54.2 135.5 9.7 19.5(Example) 115b (lb-36) 4 2.42 49.8 137.8 10.9 21.2 (Example) 116b(lb-111) 4 2.42 52.7 134.2 10.8 21.3 (Example) 117b (lb-29) 4 2.42 56.3133.9 10.9 21.3 (Example) 118b (lb-104) 4 2.42 45.9 134.1 10.7 21.7(Example) 119b (lb-31) 4 2.42 56 135.9 10.7 21.6 (Example) 120b (lb-106)4 2.42 58.3 136.1 10.7 21.9 (Example) 121b (lb-6) 4 2.42 57.4 135.5 11.121.4 (Example) 122b (lb-81) 4 2.42 56.5 132.9 11.2 21.5 (Example) 123b(lb-75) 4 2.42 55.9 133.7 11.2 21.7 (Example) 124b (lb-150) 4 2.42 54.2134.8 11.2 21.9 (Example) 125b (lb-41) 4 2.42 55.1 131.5 11.4 22(Example) 126b (lb-116) 4 2.42 54.9 130.7 11.3 22.2 (Example) 127b(lb-67) 4 2.42 53.2 137.2 11.5 22.3 (Example) 128b (lb-142) 4 2.42 49.8133.6 11.6 22.1 (Example) 129b (lb-24) 4 2.42 48.4 134.2 11.7 22.4(Example) 130b (lb-99) 4 2.42 50.6 136.4 11.8 22.5 (Example) 131b(lb-151) 4 2.42 52.1 135.1 11.8 22.6 (Example) 132b (lb-153) 4 2.42 54.3137.3 11.8 22.5 (Example) 133b (lb-73) 4 2.42 55.7 137.6 12 22.7(Example) 134b (lb-148) 4 2.42 54 136.5 12.2 22.7 (Example) 135b (lb-74)4 2.42 48.5 138.1 12.2 22.8 (Example) 136b (lb-149) 4 2.42 49.2 137.312.4 23.1 (Example) 137b (IIIb-6) 4 2.42 50.1 132.2 13.4 24 (Example)138b (IIb-6) 4 2.42 52.6 130.8 13.4 24.3 (Example) 139b (IIb-14) 4 2.4254.6 131.7 13.6 24.5 (Example) 140b (IIb-16) 4 2.42 56.3 130.9 13.5 24.7(Example) 141b (IIb-9) 4 2.42 59.6 131.3 13.6 24.5 (Example) 142b(IIIb-1) 4 2.42 51.9 129.7 13.7 24.6 (Example) 143b (IVb-1) 4 2.42 53.6138.5 13.8 24.8 (Example) 144b — 0 2.42 44.7 126 16.8 26.4 Comparativeexample) 145b Comparative 4 2.42 60.2 140.3 14.5 26.1 Comparativecompound 1b example)

TABLE 16 Film No. Cellulose acylate (Example/ Additive resin Opticalcharacteristics of film Comparative Amount Degree of acetyl Re Rth Δ ReΔ Rth example) Compound [Parts by mass] substitution [nm] [nm] [nm] [nm]146b (lb-3) 4 2.86 7.6 22.8 9.7 20.1 (Example) 147b (lb-78) 4 2.86 5.124.7 9.8 21.3 (Example) 148b (lb-9) 4 2.86 8.9 21 9.5 20.5 (Example)149b (lb-84) 4 2.86 5.7 11.8 9.4 19.9 (Example) 150b (lb-11) 4 2.86 10.226.8 9.5 21.4 (Example) 151b (lb-86) 4 2.86 7.6 27.1 9.7 22.3 (Example)152b (lb-25) 4 2.86 9.7 26.1 9.8 22.7 (Example) 153b (lb-100) 4 2.8610.7 24.3 9.7 21.3 (Example) 154b (lb-151) 4 2.86 7.6 28.6 11 23.5(Example) 155b — 0 2.86 -10.4 13 12.7 27.5 (Comparative example) 156bComparative 4 2.86 10.2 25.4 12.5 26.4 (Comparative compound 1b example)157b (lb-9) 2 2.42 51.4 130.9 9.3 18.2 (Example) (lb-84) 2 158b (lb-9) 22.42 56.3 145.8 8.4 15.8 (Example) Reference 2 compound 1 159b (lb-84) 22.42 56.2 144.9 8.3 15.7 (Example) Reference 2 compound 1 160b (lb-9)1.8 2.42 52.3 132.1 8.8 16.5 (Example) (lb-84) 1.8 Reference 0.4compound 1 161b (lb-9) 1 2.42 56.4 145.2 8.2 15.6 (Example) (lb-84) 1Reference 2 compound 1 162b (lb-9) 0.25 2.42 65.5 158.6 6.7 13.4(Example) Reference 3.75 compound 1 163b (lb-84) 0.25 2.42 65.8 160.76.7 13.4 (Example) Reference 3.75 compound 1 164b (lb-9) 0.2 2.42 64.1159.2 6.5 13.5 (Example) (lb-84) 0.2 Reference 3.6 compound 1 165b(lb-11) 2 2.42 54.3 135.1 9.5 18.6 (Example) (lb-86) 2

TABLE 17 Film No. Cellulose acylate (Example/ Additive resin Opticalcharacteristics of film Comparative Amount Degree of acetyl Re Rth Δ ReΔ Rth example) Compound [Parts by mass] substitution [nm] [nm] [nm] [nm]166b (Example) (lb-11) 2 2.42 54.1 138.4 8.6 15.7 Reference 2 compound 2167b (Example) (lb-86) 2 2.42 53.8 139.2 8.5 15.7 Reference 2 compound 2168b (Example) (lb-11) 1.5 2.42 54.1 138.8 8.6 15.8 (lb-86) 1.5Reference 1 compound 2 169b (Example) (lb-11) 1 2.42 54.7 138.7 8.5 15.6(lb-86) 1 Reference 2 compound 2 170b (Example) (lb-11) 0.5 2.42 51.9156.8 6.6 12.9 Reference 3.5 compound 2 171b (Example) (lb-86) 0.5 2.4251.7 156.5 6.6 12.8 Reference 3.5 compound 2 172b (Example) (lb-11) 0.22.42 51.4 156.5 6.6 12.8 (lb-86) 0.2 Reference 3.6 compound 2 173b(Example) (lb-25) 2 2.42 54.5 131.4 9.8 19.0 (lb-100) 2 174b (Example)(lb-25) 2 2.42 58.4 146.7 8.3 16.1 Reference 2 compound 3 175b (Example)(lb-100) 2 2.42 58.5 146.1 8.2 16.2 Reference 2 compound 3 176b(Example) (lb-25) 1.5 2.42 58.1 146.5 8.1 16.1 (lb-100) 1.5 Reference 1compound 3 177b (Example) (lb-25) 1 2.42 57.9 146.7 8.2 16.2 (lb-100) 1Reference 2 compound 3 178b (Example) (lb-25) 0.2 2.42 62.8 161.8 6.813.1 Reference 3.8 compound 3 179b (Example) (lb-100) 0.2 2.42 62.7162.1 6.7 13.0 Reference 3.8 compound 3 180b (Example) (lb-25) 0.2 2.4262.3 161.1 6.8 13.0 (lb-100) 0.2 Reference 3.6 compound 3 181b (Example)Mixture b-A 4 2.42 63.4 163.2 6.5 12.8 182b (Reference Reference 4 2.4264.3 162.8 6.5 13.4 example) compound 1 183b (Reference Reference 4 2.4252.9 142.1 6.6 12.8 example) compound 2 184b (Reference Reference 4 2.4262.9 161.4 6.8 13.0 example) compound 3

The results shown in the tables above demonstrate that all polymer filmsof examples of the present invention have increased retardation bycontaining the compounds of Formula (I) and also have reduced humiditydependency of retardation compared to the comparative example filmhaving increased retardation by containing comparative compound 1. It isdemonstrated that the effects are synergistically enhanced by adding twoor more compounds of Formula (I) to a film or by adding a referencecompound represented by Formula (6) or (7) together with a compound ofFormula (I) to a film.

Example 2b-1 Preparation of Cellulose Acylate Solution for FilmFormation (Preparation of Cellulose Acylate Solution for Film Formation)

The exemplary compounds shown in the table below were mixed withcellulose acylate resins having degrees of acetyl substitution shown inthe table based on 100 parts by mass of the cellulose acylate resins,and the compounds were each dissolved in a solvent composed of 396 partsby mass of methylene chloride and 59 parts by mass of methanol toprepare a cellulose acylate (specifically, cellulose acetate) solution.

(Casting)

The cellulose acylate solutions prepared above were each casted with aglass plate casting machine, followed by drying with hot air having acharge air temperature of 70° C. for 6 minutes. The films were peeledoff from the glass plates, were fixed to frames, and were dried with hotair having a charge air temperature of 100° C. for 10 minutes and thenwith hot air having a charge air temperature of 140° C. for 20 minutesto produce cellulose acylate films each having a thickness of 55 μm.

An additive-free film was produced as a comparative example film.Separately, a comparative example film containing an additive ofcomparative compound 1 was produced.

Optical characteristics were evaluated as in Example 1b except that thechange in retardation value depending on humidity was evaluated byhumidification at a relative humidity of 30% at 25° C. and at a relativehumidity of 80% at 25° C. for 12 hours.

TABLE 18 Film No. Cellulose acylate (Example/ Additive resin Opticalcharacteristics of film Comparative Amount Degree of acetyl Re Rth Δ ReΔ Rth example) Compound [Parts by mass] substitution [nm] [nm] [nm] [nm]185b (lb-100) 6 2.86 1.5 67.2 0.4 16.4 (Example) 186b — 0 2.86 0.2 33.10.2 20.7 (Comparative example) 187b Comparative 6 2.86 1.7 65.4 0.4 18.7(Comparative compound 1b example)

The results shown in the tables above demonstrate that all polymer filmsof examples of the present invention have increased retardation bycontaining the compounds of Formula (I) and also have reduced humiditydependency of retardation compared to the film containing a comparativecompound 1.

Example 2b-2 Preparation of Cellulose Acylate Solution for FilmFormation

Cellulose acetate films were produced as in Example 2b-1 except that thedegree of substitution of cellulose acylate, the type and amount ofadditive, the stretching temperature, the stretching ratio, and thethickness of each film were as shown in the following table.

Optical characteristics were evaluated as in Example 1b.

TABLE 19 Film No. Additive Other additive Cellulose acylate resin(Example/ Amount Amount Degree of Degree of Optical characteristics offilm Comparative [Parts by [Parts by acetyl propionyl StretchingThickness Re Rth Δ Re Δ Rth example) Compound mass] Compound mass]substitution substitution condition [μm] [nm] [nm] [nm] [nm] 188b(lb-100) 8 Poly- 15 2.42 0 180° C. 35% 65 81 224 5.4 16 (Example)condensation ester A 189b — 0 Poly- 15 2.42 0 180 ° C. 35% 65 66 168 9.926 (Comparative condensation example) ester A 190b (lb-100) 6 Saccharose6 1.5 0.85 135° C. 40% 45 50 124 7.4 20 (Example) benzoate 191b — 0Saccharose 6 1.5 0.85 135° C. 40% 45 49 126 11 25 (Comparative benzoateexample) 192b Comparative 8 Poly- 15 2.42 0 180 ° C. 35% 65 84 232 9.526 (Comparative compound condensation example) 1b ester AIn the table, polycondensation ester A is a copolymer of terephthalicacid/succinic acid/ethanediol/propanediol in a ratio of 55/45/50/50.

Example 3b Production of Cellulose Acylate Film (Preparation ofCellulose Acylate Solution for Film Formation)

The composition shown below was put in a mixing tank, followed bystirring to dissolve each component to prepare a cellulose acylatesolution 401.

TABLE 20 Composition of cellulose acylate solution 401 Cellulose acetatehaving a degree of acetyl 100.0 parts by mass substitution of 2.43 and adegree of polymerization of 340: Compound (Ib-100): 4.0 parts by massMethylene chloride (first solvent): 402.0 parts by mass Methanol (secondsolvent): 60.0 parts by mass

(Casting, Stretching)

The cellulose acylate solution 401 was casted with a band castingmachine, followed by drying until the remaining solvent content reached40%. The formed web film was peeled off from the band. When theremaining solvent content reached 20% under conditions of 140° C., thefilm was stretched in cross-direction by an elongation percentage of 30%with a tenter and was then maintained at 130° C. for 3 minutes.Subsequently, the clips holding the film were removed, and the film wasdried at 130° C. for 30 minutes to produce a cellulose acylate film401a. The film thickness was 60 μm.

An additive-free film (cellulose acylate film 402a) was produced as acomparative example film. Separately, a comparative example film(cellulose acylate film 403a) containing an additive of comparativecompound 1 was produced.

(Evaluation of Optical Characteristics)

Optical characteristics were evaluated as in Example 1b.

In the cellulose acylate film 401a containing a compound of the presentinvention, the humidity dependency of retardation was reduced comparedto those of cellulose acylate films 402a and 403a.

Example 4b Evaluation of Solution Stability

Each compound (1 part by mass) shown in the following table wasdissolved in methylene chloride (87 parts by mass) and methanol (13parts by mass). The solution was left to stand in a pressure resistantvessel at 80° C. for 66 hours, and then the compound was quantitativelymeasured by liquid chromatography to calculate the residual percentage.The results are shown in the table.

TABLE 21 Compound Residual ratio (%) Example (Ib-1) >95 Example(Ib-3) >95 Example (Ib-9) >95 Example (Ib-11) >95 Example (Ib-25) >95Example (Ib-76) >95 Example (Ib-78) >95 Example (Ib-84) >95 Example(Ib-86) >95 Example (Ib-100) >95 Example (Ib-151) >95 Example(Ib-153) >95 Comparative (A-1) 58 example Comparative (A-2) 54 example

Comparative compound A-1: The compound was synthesized in accordancewith the method described in Gazzetta Chimica Italiana (1935), 65,566-88.

Comparative compound A-2: The compound is described in Japanese PatentLaid-Open No. 2007-138119 and was synthesized in accordance with themethod described in Gazzetta Chimica Italiana (1935), 65, 566-88.

The results shown in the table demonstrate that the compound group B ofthe present invention shows high solution stability.

DESCRIPTION OF SYMBOLS

-   1 top substrate of liquid crystal cell-   3 bottom substrate of liquid crystal cell-   5 liquid crystal layer (liquid crystal molecules)-   8 a, 8 b protective film of polarizing plate-   9 a, 9 b absorption axis of protective film of polarizing plate-   10 a, 10 b phase difference film (polymer film of the present    invention)-   11 a, 11 b absorption axis of phase difference film (polymer film of    the present invention)-   P1, P2 polarizing plate-   LC liquid crystal cell

What is claimed is:
 1. A compound represented by Formula (7-1) or ahydrate of the compound, a solvate of the compound, or a salt of thecompound:

wherein in Formula (7-1), Y represents —N— or —C(-Q^(d)-R^(d))—, Q^(d)represents a single bond or a divalent linking group, and R^(d)represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynylgroup, an aryl group, a cyano group, a halogen group, or a heterocyclicgroup; Q^(aa) represents a single bond or —O—, —S—, —NH—, or —N(R)—(wherein R is an alkyl group having 1 to 8 carbon atoms); R^(aa)represents a hydrogen atom, a halogen atom, or an alkyl group having 1to 8 carbon atoms, and R^(d) and R^(aa) are optionally bonded to eachother to form a ring structure; and R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶each independently represent a hydrogen atom, a halogen atom, acarbamoyl group, a sulfamoyl group, an alkyl group having 1 to 8 carbonatoms, or an alkoxy group having 1 to 8 carbon atoms.
 2. A compoundrepresented by Formula (7-2) or a hydrate of the compound, a solvate ofthe compound, or a salt of the compound:

wherein in Formula (7-2), Y represents —N— or —C(-Q^(d)-R^(d))—, Q^(d)represents a single bond or a divalent linking group, and R^(d)represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynylgroup, an aryl group, a cyano group, a halogen group, or a heterocyclicgroup; Q^(a) represents a single bond or a divalent linking group;R^(a7) represents an alkyl group having 1 to 8 carbon atoms, and R^(d)and R^(a7) are optionally bonded to each other to form a ring; and R¹¹,R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ each independently represent a hydrogenatom, a halogen atom, a carbamoyl group, a sulfamoyl group, an alkylgroup having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8carbon atoms.
 3. The compound or a hydrate of the compound, a solvate ofthe compound, or a salt of the compound according to claim 1, thecompound being represented by Formula (8), Formula (9), or Formula (10):

wherein R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ each independently represent ahydrogen atom, a halogen atom, a carbamoyl group, a sulfamoyl group, analkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8carbon atoms; and R^(a8), R^(a9), and R^(a10) each independentlyrepresent an alkyl group having 1 to 8 carbon atoms.
 4. The compound ora hydrate of the compound, a solvate of the compound, or a salt of thecompound according to claim 3, R^(a8), R^(a9), and R^(a10) eachindependently represent an alkyl group having 1 to 4 carbon atoms.
 5. Acompound represented by Formula (IIIc), Formula (IVc), or Formula (Vf′)or a hydrate of the compound, a solvate of the compound, or a salt ofthe compound:

wherein in Formula (IIIc), Q^(a) represents a single bond or a divalentlinking group; R^(a) represents a hydrogen atom, an alkyl group, analkenyl group, an alkynyl group, an aryl group, a cyano group, a halogengroup, or a heterocyclic group; and R⁹ represents —O—Ar, an alkyl group,an alkenyl group, an alkynyl group, an aryl group, or a heterocyclicgroup, wherein Ar represents an aryl group;

wherein symbols in Formula (IVc) are each synonymous with those inFormula (IIIc);

wherein R¹¹, R¹², and R¹³ each independently represent a hydrogen atom,a nitro group, a carbamoyl group, an N-alkylcarbamoyl group having 1 to8 carbon atoms, an N,N-dialkylcarbamoyl group having 1 to 16 carbonatoms, a sulfamoyl group, an N-alkylsulfamoyl group having 1 to 8 carbonatoms, an N,N-dialkylsulfamoyl group having 1 to 16 carbon atoms, analkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16carbon atoms, an alkylamino group having 1 to 16 carbon atoms, adialkylamino group having 1 to 16 carbon atoms, or an alkoxyalkyloxygroup having 1 to 16 carbon atoms, provided that at least one of R¹¹,R¹², and R¹³ represents a substituent other than a hydrogen atom.
 6. Thecompound or a hydrate of the compound, a solvate of the compound, or asalt of the compound according to claim 5, wherein Q^(a) represents asingle bond or —O—, —NH—, or —N(R)— (wherein R is an alkyl group having1 to 8 carbon atoms); and R^(a) represents a hydrogen atom, a halogenatom, or an alkyl group having 1 to 8 carbon atoms.
 7. A compoundrepresented by Formula (IIIf), Formula (IIIg), Formula (IIIh), Formula(IVf), Formula (IVg), or Formula (IVh) or a hydrate of the compound, asolvate of the compound, or a salt of the compound:

wherein in Formula (IIIf), R^(a7) represents an alkyl group having 1 to8 carbon atoms; and R⁶, R⁷, and R⁸ each independently represent ahydrogen atom, a halogen atom, a nitro group, a cyano group, a carbamoylgroup, an N-alkylcarbamoyl group having 1 to 8 carbon atoms, anN,N-dialkylcarbamoyl group having 1 to 16 carbon atoms, a sulfamoylgroup, an N-alkylsulfamoyl group having 1 to 8 carbon atoms, anN,N-dialkylsulfamoyl group having 1 to 16 carbon atoms, an alkyl grouphaving 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbonatoms, an alkylamino group having 1 to 16 carbon atoms, a dialkylaminogroup having 1 to 16 carbon atoms, or an alkoxyalkyloxy group having 1to 16 carbon atoms;

wherein symbols in Formula (IIIg) are each synonymous with those inFormula (IIIf);

wherein symbols in Formula (IIIh) are each synonymous with those inFormula (IIIf);

wherein symbols in Formula (IVf) are each synonymous with those inFormula (IIIf);

wherein symbols in Formula (IVg) are each synonymous with those inFormula (IIIf);

wherein symbols in Formula (IVg) are each synonymous with those inFormula (IIIf).
 8. A hydrate of the compound or a solvate of thecompound according to claim
 1. 9. A hydrate of the compound according toclaim
 1. 10. A method of producing a compound represented by Formula(7-1) or a salt of the compound, a hydrate of the compound, or a solvateof the compound, which comprises reacting with a compound represented byFormula (7a), a compound represented by a scheme, and represented byFormula (7b):

wherein in Formula (7a) and Formula (7b), Q^(aa) represents a singlebond or —O—, —S—, —NH—, or —N(R)— (wherein R is an alkyl group having 1to 8 carbon atoms); R^(aa) represents a hydrogen atom, a halogen atom,or an alkyl group having 1 to 8 carbon atoms; R¹⁴, R¹⁵, and R¹⁶ eachindependently represent a hydrogen atom, a halogen atom, a carbamoylgroup, a sulfamoyl group, an alkyl group having 1 to 8 carbon atoms, oran alkoxy group having 1 to 8 carbon atoms; and Z represents a halogenatom, a hydroxy group, an alkoxy group, aryloxy group, or an acyloxygroup.
 11. The method according to claim 10, further comprising:crystallizing the compound represented by Formula (7-2) from water or anorganic solvent to yield the hydrate of the compound represented byFormula (7-1) or solvate of the compound.